JPH07288185A - Organic thin film electroluminescent (el) element - Google Patents
Organic thin film electroluminescent (el) elementInfo
- Publication number
- JPH07288185A JPH07288185A JP6104295A JP10429594A JPH07288185A JP H07288185 A JPH07288185 A JP H07288185A JP 6104295 A JP6104295 A JP 6104295A JP 10429594 A JP10429594 A JP 10429594A JP H07288185 A JPH07288185 A JP H07288185A
- Authority
- JP
- Japan
- Prior art keywords
- light emitting
- film
- thin film
- emitting layer
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 58
- 239000010408 film Substances 0.000 claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229910052738 indium Inorganic materials 0.000 claims abstract description 36
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims description 95
- 238000002347 injection Methods 0.000 claims description 41
- 239000007924 injection Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000012546 transfer Methods 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 230000005674 electromagnetic induction Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- -1 polyethylene Polymers 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 229920006267 polyester film Polymers 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 125
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000005036 potential barrier Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910019015 Mg-Ag Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 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 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000013585 weight reducing agent 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
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8052—Cathodes
-
- 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
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は，面光源等に用いられる
有機薄膜ＥＬ（エレクトロルミネッセンス）素子の構造
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure of an organic thin film EL (electroluminescence) element used for a surface light source or the like.
【０００２】[0002]
【従来の技術】有機半導体を使った発光素子は，有機蛍
光体を対向電極に挟んで構成されており，一方の電極か
ら注入された電子と，もう一方の電極から注入された正
孔が，発光層内で再結合するときに発光する。このよう
な素子は，発光体として１９６３年にＭ．Ｐｏｐｅ，
Ｈ．Ｐ．Ｋａｌｌｍａｎｎ等によりアントラセンの単結
晶に直流電圧を印加すると発光がおこることが見いださ
れた。その後，１９８７年にＫＯＤＡＫ社のＴ．Ｗ．Ｔ
ａｎｇ等により有機薄膜積層構造を利用した有機薄膜Ｅ
Ｌ素子として発表されている。そして，その後，このモ
デルを中心に研究開発が活発に行なわれて，現在に至っ
ている。その代表構造を図５に示す。従来の構造は，有
機薄膜の積層構造からなる発光層の形成に際して，真空
蒸着法等の真空成膜技術を使う必要があったため，設備
投資が大きくなり，また，製造工程に難点があり，コス
トの面でも望ましくなかった。さらに，封止枠を形成
し，窒素ガスを封入した構造のために，薄型化の要請に
対応できなかった。2. Description of the Related Art A light emitting device using an organic semiconductor is constructed by sandwiching an organic phosphor between opposing electrodes, and electrons injected from one electrode and holes injected from the other electrode are It emits light when it recombines in the light emitting layer. Such an element was used as a luminous body in 1963 by M.M. Pope,
H. P. It was found by Kallmann et al. That light emission occurs when a DC voltage is applied to a single crystal of anthracene. After that, in 1987, T.K. W. T
Organic thin film E using an organic thin film laminated structure by ang etc.
It is announced as an L element. Since then, research and development have been actively carried out centering on this model, and have reached the present. The representative structure is shown in FIG. In the conventional structure, when forming a light emitting layer composed of a laminated structure of organic thin films, it is necessary to use a vacuum film forming technique such as a vacuum vapor deposition method, resulting in a large capital investment and a difficulty in the manufacturing process. It was not desirable in terms of. In addition, because of the structure in which the sealing frame is formed and nitrogen gas is enclosed, it is not possible to meet the demand for thinning.
【０００３】上記の構成に対して，本発明者は，特願平
５−３１９２７０号において図６あるいは図７に示すよ
うに，真空成膜技術を用いずに発光層を形成するととも
に，防湿フイルムにより封止することによって，生産性
を向上させ，コストの低減，薄型化，軽量化を可能にし
た有機薄膜ＥＬ素子を提案している。すなわち，図６に
示すものは，有機発光体層２ｃと正孔注入材料層３とを
積層にして，正孔注入材料層３側に陽極（透明電極）５
を配し，有機発光体層２ｃ側に陰極（背面電極）１を配
する。そして，その上下を吸湿フイルム８で挟み，更
に，その上下を防湿フイルム９で挟み，最後に全体をラ
ミネートして構成する。あるいは，図７に示すように，
パネル化するにあたり，有機発光体層２ｃと正孔注入材
料層３の材料と必要に応じた結合剤を混ぜて発光層２と
することもできる。With respect to the above structure, the inventor of the present invention, as shown in FIG. 6 or 7 in Japanese Patent Application No. 5-319270, forms a light emitting layer without using a vacuum film forming technique, and also has a moisture-proof film. We have proposed an organic thin-film EL device that improves productivity and enables cost reduction, thinning, and weight reduction by encapsulating. That is, in the structure shown in FIG. 6, the organic light emitting layer 2c and the hole injection material layer 3 are laminated, and the anode (transparent electrode) 5 is provided on the hole injection material layer 3 side.
And the cathode (back electrode) 1 on the organic light emitting layer 2c side. Then, the upper and lower sides thereof are sandwiched by a moisture absorbing film 8, the upper and lower sides thereof are sandwiched by a moisture-proof film 9, and finally the whole is laminated. Alternatively, as shown in FIG.
In forming a panel, the material of the organic light emitting layer 2c and the hole injection material layer 3 and a binder as required may be mixed to form the light emitting layer 2.
【０００４】[0004]
【発明が解決しようとする課題】ところが，このような
有機薄膜ＥＬ素子においては，陽極または陰極の上に発
光層を塗布し，次いで発光層の上に陰極または陽極を積
層する際に，発光層の塗膜表面が完全に乾燥してしまう
ので，後から発光層上に積層する電極と発光層の接合が
不完全になって接触抵抗が高くなり，発光輝度や発光効
率の低下が生じやすい，という問題があった。また，陰
極としてＡｌ箔にＭｇ−Ａｇ等の金属膜をスパッタ等の
真空成膜技術で形成した金属フイルムを用いているため
に，設備投資に伴い製造コストが高くなることや生産性
が低い点が問題となっていた。However, in such an organic thin film EL device, when a light emitting layer is applied on an anode or a cathode and then a cathode or an anode is laminated on the light emitting layer, the light emitting layer is formed. Since the surface of the coating film is completely dried, the contact between the electrode and the light emitting layer, which will be laminated on the light emitting layer later, is incomplete, resulting in high contact resistance, which tends to cause a decrease in light emission brightness and light emission efficiency. There was a problem. In addition, since a metal film formed by depositing a metal film such as Mg-Ag on an Al foil by a vacuum film forming technique such as sputtering is used as a cathode, the manufacturing cost increases due to equipment investment and the productivity is low. Was a problem.
【０００５】本発明は，上記の問題点を解決し，発光輝
度，発光効率を高めた，生産性，コスト，薄型光源，軽
量光源，自由形状の光源を得るフイルム状有機薄膜ＥＬ
素子を提供する。The present invention solves the above-mentioned problems and enhances the luminous brightness and luminous efficiency of the film-like organic thin film EL to obtain a productivity, cost, a thin light source, a light source, and a free-form light source.
Provide the element.
【０００６】[0006]
【課題を解決するための手段】本発明の請求項１記載の
手段は，有機発光体を含む発光層に陽極より正孔を注入
し，陰極より電子を注入することにより発光させる有機
薄膜ＥＬ素子であり，前記発光層を陽極及び陰極で挟み
込み，その両側に防湿層を配設した有機薄膜ＥＬ素子に
おいて，陰極として仕事関数の小さい金属膜を前記発光
層上に溶融接着したことを特徴とする有機薄膜ＥＬ素子
である。本発明の請求項２記載の手段は，発光層は，陽
極側から陰極側に向かって，正孔注入材料層，有機発光
体層，電子注入材料層が順に積層されていることを特徴
とする請求項１記載の有機薄膜ＥＬ素子である。本発明
の請求項３記載の手段は，発光層は，正孔注入材料，有
機発光体，電子注入材料が混合された層であることを特
徴とする請求項１記載の有機薄膜ＥＬ素子である。本発
明の請求項４記載の手段は，発光層は，陽極側から陰極
側に向かって，正孔注入材料の性質を兼ね備えた有機発
光体層と電子注入材料層とが順に積層されていることを
特徴とする請求項１記載の有機薄膜ＥＬ素子である。本
発明の請求項５記載の手段は，発光層は，陽極側から陰
極側に向かって，正孔注入材料と有機発光体が混合され
た層と，電子注入材料層とが順に積層されていることを
特徴とする請求項１記載の有機薄膜ＥＬ素子である。本
発明の請求項６記載の手段は，発光層は，陽極側から陰
極側に向かって，正孔注入材料層と，電子注入材料の性
質を兼ね備えた有機発光体層とが順に積層されているこ
とを特徴とする請求項１記載の有機薄膜ＥＬ素子であ
る。本発明の請求項７記載の手段は，発光層は，陽極側
から陰極側に向かって，正孔注入材料層と，有機発光体
と電子注入材料が混合された層とが順に積層されている
ことを特徴とする請求項１記載の有機薄膜ＥＬ素子であ
る。本発明の請求項８記載の手段は，有機発光体を含む
発光層に陽極より正孔を注入し，陰極より電子を注入す
ることにより発光させる有機薄膜ＥＬ素子であり，前記
発光層を陽極及び陰極で挟み込み，その両側に防湿層を
配設した有機薄膜ＥＬ素子の製造方法において，陽極上
に発光層を形成する工程と，支持体フイルム上に設けた
仕事関数の小さい金属膜を前記発光層面に転写して陰極
を形成する工程を含むことを特徴とする有機薄膜ＥＬ素
子の製造方法である。本発明の請求項９記載の手段は，
仕事関数の小さい金属膜が，金属インジウムからなるこ
とを特徴とする請求項８記載の有機薄膜ＥＬ素子の製造
方法である。本発明の請求項１０記載の手段は，金属イ
ンジウムが，膜厚３．５±０．５μｍで支持体フイルム
上に設けられ，純度４Ｎであることを特徴とする請求項
９記載の有機薄膜ＥＬ素子の製造方法である。本発明の
請求項１１記載の手段は，金属インジウムの転写が，金
属インジウムの溶融接着により行われることを特徴とす
る請求項９記載の有機薄膜ＥＬ素子の製造方法である。
本発明の請求項１２記載の手段は，金属インジウムの溶
融接着を，熱ラミネーター方式（例えば，上下に電磁誘
導加熱ロ−ラで構成した熱ロ−ラ間を通す方式）で行う
ことを特徴とする請求項１１記載の有機薄膜ＥＬ素子の
製造方法である。According to a first aspect of the present invention, an organic thin film EL element is provided which emits light by injecting holes from an anode and electrons from a cathode into a light emitting layer containing an organic light emitter. In the organic thin-film EL device in which the light emitting layer is sandwiched by an anode and a cathode, and a moisture-proof layer is provided on both sides of the anode and the cathode, a metal film having a small work function as a cathode is melt-bonded onto the light emitting layer. It is an organic thin film EL device. According to a second aspect of the present invention, in the light emitting layer, a hole injecting material layer, an organic light emitting layer, and an electron injecting material layer are sequentially stacked from the anode side toward the cathode side. The organic thin film EL element according to claim 1. The means according to claim 3 of the present invention is the organic thin film EL element according to claim 1, wherein the light emitting layer is a layer in which a hole injection material, an organic light emitting material, and an electron injection material are mixed. . According to a fourth aspect of the present invention, in the light emitting layer, an organic light emitting layer having a property of a hole injecting material and an electron injecting material layer are sequentially laminated from the anode side to the cathode side. The organic thin film EL device according to claim 1, wherein According to a fifth aspect of the present invention, in the light emitting layer, a layer in which a hole injection material and an organic light emitting material are mixed and an electron injection material layer are sequentially stacked from the anode side toward the cathode side. The organic thin film EL element according to claim 1, wherein According to a sixth aspect of the present invention, in the light emitting layer, a hole injecting material layer and an organic light emitting layer having a property of an electron injecting material are sequentially laminated from the anode side to the cathode side. The organic thin film EL element according to claim 1, wherein According to a seventh aspect of the present invention, in the light emitting layer, a hole injection material layer and a layer in which an organic light emitting material and an electron injection material are mixed are sequentially laminated from the anode side toward the cathode side. The organic thin film EL element according to claim 1, wherein The means according to claim 8 of the present invention is an organic thin film EL device which emits light by injecting holes from an anode and electrons from a cathode into a light emitting layer containing an organic light emitting body, wherein the light emitting layer comprises an anode and In a method of manufacturing an organic thin film EL device sandwiched by a cathode and having moisture-proof layers on both sides thereof, a step of forming a light emitting layer on an anode, and a metal film having a small work function provided on a support film are provided on the light emitting layer surface. The method for producing an organic thin film EL element is characterized by including the step of transferring to a cathode to form a cathode. According to claim 9 of the present invention,
9. The method for manufacturing an organic thin film EL element according to claim 8, wherein the metal film having a low work function is made of indium metal. 10. The organic thin film EL according to claim 9, wherein the indium metal is provided on the support film with a film thickness of 3.5 ± 0.5 μm and has a purity of 4N. It is a method of manufacturing an element. The means according to claim 11 of the present invention is the method for manufacturing an organic thin film EL element according to claim 9, wherein the transfer of the metal indium is performed by fusion bonding of the metal indium.
According to a twelfth aspect of the present invention, the fusion bonding of the metal indium is performed by a thermal laminator method (for example, a method of passing between heat rollers composed of an electromagnetic induction heating roller at the top and bottom). The method of manufacturing an organic thin film EL element according to claim 11.
【０００７】以下，図面を用いて本発明の各構成要素の
詳細を説明する。図１は，本発明の有機薄膜ＥＬ素子の
実施例について，防湿フイルムの一部を切除して示す模
式的な斜視図である。本実施例の有機薄膜ＥＬ素子は，
陽極５の上に発光層２が形成されており，発光層２の上
には金属インジウムの薄膜が転写されて陰極１が形成さ
れている。陽極５と陰極１には，それぞれ電極リード７
が固定テープ１０により取り付けられている。このよう
に積層された陽極５，発光層２，陰極１は２枚の防湿フ
イルム９によって両側から封止されている。Details of each component of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic perspective view showing an organic thin film EL element according to an embodiment of the present invention with a part of a moisture-proof film cut away. The organic thin film EL device of this embodiment is
The light emitting layer 2 is formed on the anode 5, and the thin film of metal indium is transferred on the light emitting layer 2 to form the cathode 1. Each of the anode 5 and the cathode 1 has an electrode lead 7
Are attached by a fixing tape 10. The anode 5, the light emitting layer 2, and the cathode 1 thus laminated are sealed from both sides by two moisture-proof films 9.
【０００８】本発明の有機薄膜ＥＬ素子の発光機構は，
無機薄膜ＥＬ素子及び粉末分散型ＥＬ素子の電界発光タ
イプと異なり，注入発光タイプであり電極から電荷を注
入するので，電極の材料選択が難しい。すなわち，この
有機薄膜ＥＬ材料は，一般に半絶縁性であるため材料自
身には，キャリヤが存在しない。電流に寄与するキャリ
ヤの大部分は金属電極から，金属界面／有機薄膜ＥＬ層
を乗り越えて注入される。更に，各層間の界面にも電位
障壁が存在し，これを乗り越えて流れる必要がある。そ
して，この界面の接合部において，電位障壁の高さ自身
は変化せず，キャリヤは熱放出，電界放出，トンネル等
の手段でこのバリアを乗り越えて移動する必要がある。
そこで，陰極は，仕事関数の小さな金属（目安として
４．０ｅＶ以下）またはその合金の電気導電性化合物
で，イオン化ポテンシャルが小さく，電子親和力が大き
い材料が使われる。例えば，Ｍｇ，Ｃａ等のII族化合
物, Ｇａ，ＩｎのIII族金属（Ｂ，Ａｌを除く）が適し
ており，一般的には，Ｍｇが広く用いることができ，Ｍ
ｇのみでは酸化が早いので，ＡｇまたはＣｕを３〜１５
％添加して，酸化を進みにくくした材料が使われる。最
適範囲の添加量は，５〜１０％である。本発明において
は，Ｉｎが，比較的低温で溶融し発光層上に転写しやす
いことから，仕事関数の小さな金属として金属インジウ
ムが好適に用いられる。The light emitting mechanism of the organic thin film EL device of the present invention is as follows.
Unlike the electroluminescence type of the inorganic thin film EL element and the powder dispersion type EL element, it is an injection emission type and charges are injected from the electrode, so it is difficult to select the electrode material. That is, since the organic thin film EL material is generally semi-insulating, the material itself has no carrier. Most of the carriers that contribute to the electric current are injected from the metal electrode over the metal interface / organic thin film EL layer. In addition, there is a potential barrier at the interface between the layers, and it is necessary to flow over this potential barrier. At the junction of this interface, the height of the potential barrier itself does not change, and the carriers must move over this barrier by means of heat emission, field emission, tunneling or the like.
Therefore, the cathode is an electrically conductive compound of a metal having a small work function (4.0 eV or less as a guide) or its alloy, and a material having a small ionization potential and a large electron affinity is used. For example, Group II compounds such as Mg and Ca and Group III metals of Ga and In (excluding B and Al) are suitable. Generally, Mg can be widely used, and M
Since oxidation is fast only with g, Ag or Cu is added in an amount of 3 to 15
% Is used to prevent oxidation from progressing. The optimum amount of addition is 5 to 10%. In the present invention, since In melts at a relatively low temperature and is easily transferred onto the light emitting layer, indium metal is preferably used as a metal having a small work function.
【０００９】陰極１は，予めフイルム上に形成された金
属インジウム膜を加熱溶融させて，発光層２上に転写し
て形成したものであり，フイルム上の金属インジウムが
発光層２に接するように重ね合わせ，この状態で加熱ロ
−ル間を通過させることによって，金属インジウムの転
写を行うことができる。金属インジウムは１５７℃で溶
融するので，１６０℃程度の低温で陰極１の形成が可能
であり，有機発光体等に対する熱劣化の影響を回避する
ことができる。金属インジウムの支持体となるフイルム
は，比較的薄くて耐熱性のあるものが好ましく，四フッ
化エチレン樹脂フイルム等が適用し得る。またフイルム
上への金属インジウム膜の形成は，真空蒸着法またはス
パッタリング法により行うことができる。The cathode 1 is formed by heating and melting a metal indium film previously formed on the film and transferring it onto the light emitting layer 2, so that the metal indium on the film is in contact with the light emitting layer 2. The metal indium can be transferred by superposing and passing between the heating rolls in this state. Since the metal indium melts at 157 ° C., the cathode 1 can be formed at a low temperature of about 160 ° C., and the influence of thermal deterioration on the organic light emitting body and the like can be avoided. The film serving as a support for metallic indium is preferably relatively thin and has heat resistance, and a tetrafluoroethylene resin film or the like can be applied. Further, the formation of the metal indium film on the film can be performed by a vacuum vapor deposition method or a sputtering method.
【００１０】陽極５は，仕事関数の大きな金属またはそ
の合金の電気導電性化合物であり，イオン化ポテンシャ
ルが高く，電子親和力が小さい材料が最適である。例え
ば，Ａｕ，ＣｕＩ，ＳｎＯ2 ，ＩＴＯ，Ｐｔ，Ｓｅ，Ｔ
ｅ等が用いられ，更に光透過率の良いものが使われ，Ｉ
ＴＯが普通一般的に用いられる。The anode 5 is an electrically conductive compound of a metal having a large work function or an alloy thereof, and a material having a high ionization potential and a small electron affinity is optimal. For example, Au, CuI, SnO 2 , ITO, Pt, Se, T
e, etc. are used, and those with better light transmittance are used.
TO is commonly and commonly used.
【００１１】本発明の有機薄膜ＥＬ素子の発光層２とし
ては，図４にその構造モデルを示すすように，図４
（ｂ）が標準的で，図４（ａ）及び図４（ｃ）がその応
用構造である。まず，図４（ｂ）の構造について説明す
る。ここで，陽極５と陰極１に挟持された発光層２は陽
極５側から順に正孔注入材料層３，有機発光体層２ｂ，
電子注入材料層４からなる。発光は陽極５から正孔注入
材料層３を通過して正孔が有機発光体層２ｂに入り，陰
極１から電子注入材料層４を通過して電子が入り，有機
発光体層２ｂ内で正孔と電子との再結合が起きて，有機
発光体層２ｂ内の分子を励起させて，その励起エネルギ
を光として取り出すのである。図４（ａ）に示す構造の
有機発光体層２ａは，図４（ｂ）の各層のうち，正孔注
入材料と有機発光体との性質を兼ね備えた材料で構成す
るものであり，図４（ｃ）の有機発光体層２ｃは，図４
（ｂ）の各層のうち，有機発光体と電子注入材料との性
質を兼ね備えた材料で構成するものである。また，より
発光効率をあげるため，正孔注入材料層３と有機発光体
層２及び有機発光体層２と電子注入材料層４との間に，
それぞれ正孔障壁層，電子障壁層等を介在させた構造で
もよい。さらに，図４（ａ）に示す有機発光体層２ａ
を，有機発光体と正孔注入材料とを混合することにより
構成してもよく，図４（ｃ）に示す有機発光体層２ｃ
を，有機発光体と電子注入材料とを混合することにより
構成してもよい。また，発光層を，有機発光体，正孔注
入材料，電子注入材料が均一に混合されたバルク状の単
一層として構成すると，パネル化が容易であり，耐久性
を向上させる点で有利である。さらに，パネル化してよ
り一層，実用レベルに近づけるには，正孔注入材料，有
機発光体，電子注入材料等が十分に分子歪の発生しない
材料，すなわち，分子置換基の相互作用の少ない材料よ
りなり，また陰極は，仕事関数が小さく，酸化されにく
い材料から構成され，更に，熱的及び電気的に材料が劣
化されることのない，十分に選択された材料であること
が望ましい。その上，パネル内の水分を捕集して，外部
からの水分の侵入を防いでパネル化することにより本発
明の有機薄膜ＥＬ素子が得られ，その使用範囲が更に拡
大する。As the light emitting layer 2 of the organic thin film EL device of the present invention, as shown in the structural model of FIG.
4B is a standard, and FIG. 4A and FIG. 4C are the applied structures. First, the structure of FIG. 4B will be described. Here, the light emitting layer 2 sandwiched between the anode 5 and the cathode 1 is the hole injection material layer 3, the organic light emitting layer 2b, and the organic light emitting layer 2b in order from the anode 5 side.
The electron injection material layer 4 is formed. Light is emitted from the anode 5 through the hole injection material layer 3 into which holes enter the organic light emitting layer 2b, and from the cathode 1 through the electron injection material layer 4 into which electrons enter and are positively charged in the organic light emitting layer 2b. The holes and the electrons are recombined to excite the molecules in the organic light emitting layer 2b and extract the excitation energy as light. The organic light emitting layer 2a having the structure shown in FIG. 4 (a) is made of the material having the properties of both the hole injecting material and the organic light emitting material among the layers shown in FIG. 4 (b). The organic light emitting layer 2c shown in FIG.
Each of the layers (b) is made of a material having the properties of both an organic light emitting material and an electron injection material. Further, in order to further increase the light emission efficiency, between the hole injection material layer 3 and the organic light emitting layer 2 and between the organic light emitting layer 2 and the electron injection material layer 4,
A structure in which a hole blocking layer, an electron blocking layer, etc. are interposed may be used. Furthermore, the organic light emitting layer 2a shown in FIG.
May be formed by mixing an organic light emitting material and a hole injecting material, and the organic light emitting material layer 2c shown in FIG.
May be formed by mixing an organic light emitting material and an electron injection material. Further, when the light emitting layer is formed as a bulk single layer in which the organic light emitting material, the hole injection material and the electron injection material are uniformly mixed, it is easy to form a panel and it is advantageous in improving durability. . Furthermore, in order to bring it closer to a practical level by making it into a panel, a hole injection material, an organic luminescent material, an electron injection material, etc. are materials that do not generate sufficient molecular strain, that is, materials with less interaction of molecular substituents. It is desirable that the cathode is made of a material having a low work function and is not easily oxidized, and is a material sufficiently selected so that the material is not thermally or electrically deteriorated. In addition, the organic thin film EL element of the present invention can be obtained by collecting water in the panel to prevent entry of water from the outside to form a panel, and its range of use is further expanded.
【００１２】発光層としては，蛍光色素が用いられる。
構造によっては，正孔注入材料と電子注入材料の性質を
具備した蛍光色素が用いられる。例えば，蛍光染料，蛍
光顔料，蛍光増白剤，レーザ用染料，蛍光分析用試薬等
があり，以下の条件を満たすものが使われる。 条件；電界印加時に陽極から正孔を陰極から電子を注
入できること。 注入された電荷を移動させ，正孔と電子とが再結合す
る場を提供できること。 発光効率が高いこと。 上記の条件を満足するものとして，正孔を注入し易くす
るために，発光層のイオン化ポテンシャルは，６．０ｅ
Ｖ以下であること，また，電子を注入し易くするために
は，電子親和力が２．５ｅＶ以上であることが望まし
い。前述した図４（ａ）に示すような有機発光体層２ａ
に用いられる正孔注入材料の機能を兼ねる有機発光体と
しては，ピラゾリン２量体等が挙げられる。また，図４
（ｃ）に示すような有機発光体層２ｃに用いられる電子
注入材料の機能を兼ねる有機発光体としては，ペリレ
ン，ナフタレン，クマリン，ビススチリル，ピラジン等
が挙げられる。ただし，ここに挙げた材料については同
一の材料であっても，有機発光体として使用したり，正
孔注入材料あるいは電子注入材料として使用した例が種
々学会等で報告されており，適宜，所望のものを選択し
て用いてもよい。本発明においては，有機発光体，正孔
注入材料，電子注入材料を必要に応じて，結合剤と混合
したものを，スプレー法，スピンナ法，浸漬塗布法，ス
クリーン印刷法，ロ−ルコーター法，ＬＢ法等で電極上
に塗布することができ，真空成膜技術を用いなくてもよ
い。A fluorescent dye is used for the light emitting layer.
Depending on the structure, a fluorescent dye having the properties of a hole injection material and an electron injection material is used. For example, there are fluorescent dyes, fluorescent pigments, fluorescent whitening agents, laser dyes, fluorescent analysis reagents, etc., and those satisfying the following conditions are used. Conditions: Ability to inject holes from the anode and electrons from the cathode when an electric field is applied. It should be able to move the injected charge and provide a field where holes and electrons recombine. High luminous efficiency. To satisfy the above conditions, in order to facilitate injection of holes, the ionization potential of the light emitting layer is 6.0e.
The electron affinity is preferably 2.5 eV or more in order to be V or less and to facilitate injection of electrons. The organic light emitting layer 2a as shown in FIG.
Examples of the organic luminescent material which also has the function of the hole injecting material used in the above include a pyrazoline dimer and the like. In addition, FIG.
Examples of the organic luminescent material having the function of the electron injection material used for the organic luminescent material layer 2c as shown in (c) include perylene, naphthalene, coumarin, bisstyryl, pyrazine and the like. However, even if the materials listed here are the same, examples of using them as organic light emitters or as hole injection materials or electron injection materials have been reported in various academic societies, etc. One may be selected and used. In the present invention, a mixture of an organic light emitting material, a hole injecting material, and an electron injecting material with a binder, if necessary, is sprayed, spinner method, dip coating method, screen printing method, roll coater method, It can be applied onto the electrode by the LB method or the like, and it is not necessary to use the vacuum film forming technique.
【００１３】正孔注入材料は，陽極より注入された正孔
を有機発光体層に伝達する機能を有するもので，この層
を陽極と有機発光体層との間に置くことにより，低い電
圧で多くの正孔を有機発光体層に伝達する機能を有す
る。更に，有機発光体層と正孔注入材料層の界面に存在
する電子の障壁により，陰極から有機発光体層に注入さ
れた電子は，有機発光体層と正孔注入材料層との界面近
傍に蓄積され，発光効率が向上する。この層に用いられ
る材料は，イオン化ポテンシャルが小さく，電界印加時
に１０-6〜１０-2ｃｍ2 ／Ｖ・Ｓの移動度をもつものが
用いられる。The hole-injecting material has a function of transmitting holes injected from the anode to the organic light-emitting layer, and by placing this layer between the anode and the organic light-emitting layer, a low voltage is applied. It has a function of transmitting many holes to the organic light emitting layer. Further, due to the electron barrier existing at the interface between the organic light emitting layer and the hole injecting material layer, the electrons injected from the cathode into the organic light emitting layer are near the interface between the organic light emitting layer and the hole injecting material layer. It is accumulated and the luminous efficiency is improved. The material used for this layer has a low ionization potential and a mobility of 10 −6 to 10 −2 cm 2 / V · S when an electric field is applied.
【００１４】電子注入材料は，陰極より注入された電子
を有機発光体に伝達する機能を有し，この層を陰極と有
機発光体層の間に置くことにより，より低い電界で多く
の電子を発光体に注入できる。この電子注入材料として
は，電子受容性の物質が用いられるが，電子受容性が大
きすぎるものは，有機発光体と錯体を形成したり，有機
発光体からエネルギー移動を起こし易いため，このよう
な問題の生じないものを選択する。The electron injecting material has a function of transmitting electrons injected from the cathode to the organic luminescent material, and by placing this layer between the cathode and the organic luminescent material layer, many electrons can be emitted at a lower electric field. Can be injected into the light emitter. A substance having an electron accepting property is used as the electron injecting material, but a substance having an excessively large electron accepting property is likely to form a complex with the organic light emitting body or cause energy transfer from the organic light emitting body. Select one that does not cause a problem.
【００１５】また，本発明においては，集電効果を高め
るために，陽極の（ＩＴＯ）電極面に電極リード７と接
続する集電体を用いることができ，集電体は，陽極５か
ら有機発光体層（２ａ，２ｂ，２ｃ）に正孔を注入しや
すくするために陽極５と有機発光体層との間にに形成す
る。集電体を形成するにあたっては，パネルの面積にも
よるが，代表的には，発光面積が小さい場合には，線状
の集電体６を，発光面積が中程度の場合には，Ｌ字状の
集電体を，発光面積が大きい場合には，□型状の集電体
を配設する。集電体の材質としては，仕事関数の大きい
金属，例えば，Ａｕ，Ｔｅ，Ｐｔ，Ｓｅの他にＣｕＩが
用いられ，スパッタリング法，スクリーン印刷法等によ
り形成される。さらに，各電極と防湿層（防湿フイルム
９）との間に吸湿層を配置してもよい。Further, in the present invention, in order to enhance the current collecting effect, a current collector which is connected to the electrode lead 7 on the (ITO) electrode surface of the anode can be used. It is formed between the anode 5 and the organic light emitting layer to facilitate injection of holes into the light emitting layer (2a, 2b, 2c). When forming the current collector, it depends on the area of the panel, but typically, the linear current collector 6 is used when the light emitting area is small, and L is used when the light emitting area is medium. If the light emission area is large, a square-shaped current collector is provided. As a material of the current collector, CuI is used in addition to metal having a large work function, such as Au, Te, Pt, and Se, and is formed by a sputtering method, a screen printing method, or the like. Furthermore, a moisture absorption layer may be arranged between each electrode and the moisture-proof layer (moisture-proof film 9).
【００１６】防湿層は，外部からの水分の侵入を防ぐた
めのフイルムで，通常は三フッ化塩化エチレン樹脂膜ま
たはポリエステル樹脂のフイルム上に水分を通過させな
いバリヤー層，例えば，シリカ蒸着層や塩化ビニリデン
をコートしたものを使うこともできる。すなわち，防湿
効果を施したフイルム上に接着剤をコートし，その目的
に用いられる。The moisture-proof layer is a film for preventing the intrusion of moisture from the outside, and is usually a barrier layer that does not allow moisture to pass over the film of trifluorochloroethylene resin film or polyester resin, for example, a silica vapor deposition layer or a chloride layer. You can also use a vinylidene-coated one. That is, a film having a moisture-proof effect is coated with an adhesive and used for that purpose.
【００１７】[0017]
【作用】本発明においては，陽極上に発光層材料を塗布
して形成した発光層の面に，予め金属インジウム等の薄
膜が形成されたフイルムを，その金属インジウム膜等の
形成面が発光層に接するように重ね合わせて，金属イン
ジウム等を加熱溶融させて発光層に転写することにより
陰極を形成しているので，陰極と発光層の接合が良好に
行われ，また，前述のように，陰極として仕事関数の小
さい金属として，金属インジウム等を用いうるので，発
光輝度，発光効率の向上が可能となる。更に，金属イン
ジウム膜等が形成されたフイルムは，予め巻き取り蒸着
機等で連続的に生産しておくことにより生産性良く，比
較的安価に入手可能であり，素子を形成する際には真空
成膜技術を適用することなく，密着性の良い陰極が生産
性良く得られる。In the present invention, a film having a thin film of metal indium or the like formed in advance on the surface of the light emitting layer formed by coating the material for the light emitting layer on the anode is used. Since the cathode is formed by superimposing so that it is in contact with and heating and melting metal indium and the like and transferring it to the light emitting layer, the cathode and the light emitting layer are joined well, and as described above, Since metal indium or the like can be used as the metal having a small work function as the cathode, it is possible to improve the emission brightness and the emission efficiency. Further, the film on which the metal indium film or the like is formed has good productivity and can be obtained at a comparatively low cost by continuously producing it in advance by a winding vapor deposition machine or the like. A cathode with good adhesion can be obtained with good productivity without applying film forming technology.
【００１８】[0018]
【実施例】以下，図を用いて本発明の実施例を説明す
る。図２は本発明実施例の工程図を示し，図３は，その
要部の工程を模式的に説明する断面図であり，これを中
心にして本発明の実施例を説明する。 Ａ：ＩＴＯ切断 まず，図３（ａ）に示すように，厚さ１２５μｍのポリ
エステルフイルムの陽極支持体５ａ上に陽極材料層（Ｉ
ＴＯ膜）５ｂを付けた透明導電性フイルムを所定の寸法
に切断する。 Ｂ：剥離用フイルム貼合せ ついで，図３（ｂ）に示すように，接着剤を設けた３０
μｍのポリエチレンフイルムからなる剥離用フイルム５
０を，後工程の図３（ｆ）でＩＴＯ膜上の電極リード７
を取り付け得る面積より少し大きめのサイズとしたもの
を，電磁誘導加熱コイル付きラミネーター装置により貼
り付ける。その条件は，以下のようである。 上ロ−ラ温度： ８０℃ 下ロ−ラ温度：１００℃ 線圧力 ： １０ｋｇ／ｃｍ2 ロ−ラ速度 ： １５ｃｍ／ｍｉｎ Ｃ：発光層塗布 次に，図３（ｃ）に示すように，発光層２用の塗布液を
スピンコータにより塗布する。その条件は，数滴の塗布
液を滴下し，３５００ｒｐｍで２０ｓｅｃ間回転する。
膜厚は，３０〜５０ｎｍとなる。そして，８０℃，２０
ｍｉｎの乾燥を行う。発光層２用の塗布液は以下の成分
である。 ポリ（Ｎ−ビニルカルバゾール） １．００重量部（正孔注入材料） ペリレン ０．１３重量部（電子注入材料） クマリン ０．５０重量部（有機発光体） １，２−ジクロロエタン ５０．００重量部 塗布の方法は，スピンコータに限らず，浸漬，電気泳動
等適宜選ぶことができる。Embodiments of the present invention will be described below with reference to the drawings. FIG. 2 is a process drawing of an embodiment of the present invention, and FIG. 3 is a cross-sectional view for schematically explaining the steps of the main part of the present invention. A: ITO cutting First, as shown in FIG. 3A, an anode material layer (I) was formed on the anode support 5a of a polyester film having a thickness of 125 μm.
The transparent conductive film provided with the TO film) 5b is cut into a predetermined size. B: Laminating film for peeling Then, as shown in FIG.
Peeling film 5 consisting of μm polyethylene film
0 is the electrode lead 7 on the ITO film in FIG.
Use a laminator device with an electromagnetic induction heating coil that has a size slightly larger than the area that can be attached. The conditions are as follows. Upper roller temperature: 80 ° C. Lower roller temperature: 100 ° C. Linear pressure: 10 kg / cm 2 Roller speed: 15 cm / min C: Luminescent layer coating Next, as shown in FIG. The coating liquid for layer 2 is applied by a spin coater. The conditions are such that a few drops of the coating liquid are dropped and rotated at 3500 rpm for 20 seconds.
The film thickness is 30 to 50 nm. And 80 ℃, 20
Dry for min. The coating liquid for the light emitting layer 2 contains the following components. Poly (N-vinylcarbazole) 1.00 parts by weight (hole injection material) Perylene 0.13 parts by weight (electron injection material) Coumarin 0.50 parts by weight (organic luminescent material) 1,2-dichloroethane 50.00 parts by weight The coating method is not limited to the spin coater, and can be appropriately selected such as dipping and electrophoresis.
【００１９】Ｄ：剥離用フイルムの剥離 ついで，図３（ｄ）に示すように，上記の剥離用フイル
ム５０を剥離する。この場合，当然，その上の発光層２
も一緒に剥離し，電極リード７の取り付け部が剥き出し
になる。 Ｅ：陰極転写 次に，図示しないが，転写体６０として，厚さ１００μ
ｍの四フッ化エチレン樹脂フイルムからなる支持体フイ
ルム６０ａ上に，陰極１用の金属インジウムを真空蒸着
法により３．５±０．５μｍの厚みで成膜する。この時
の金属インジウムの剥離強度は２．６±０．７ｇ／５ｍ
ｍであった。ついで，図３（ｅ）に示すように，金属イ
ンジウム面と発光層２の面とを合わせ，電磁誘導加熱コ
イルの間を通過させて，金属インジウムを溶かして，金
属インジウムを溶融接着する。転写時の金属インジウム
の温度は，金属インジウムの融点１５７℃より少し高い
１６０℃で行われる。その時の条件は，以下のようであ
る。 上ロ−ラ温度：１５０℃ 下ロ−ラ温度：１５０〜１８０℃ 線圧力 ： ３０ｋｇ／ｃｍ2 ロ−ラ速度 ： １０ｃｍ／ｍｉｎ 溶融接着後，表面の支持体フイルム６０ａを取り去る。
また，この工程の転写は，部分転写でも前面転写でも表
示の目的を達する方法であればどらちでも良い。 Ｆ：電極リード取り付け ついで，Ｔ字形電極リード７を図示を省略した固定テー
プと共に，図３（ｆ）に示すように，陰極１（金属イン
ジウム）面の所定の位置及び前記図３（ｄ）で説明した
陽極材料層（ＩＴＯ）面の剥き出しになった電極取付部
のそれぞれに取り付ける。以上が図３の説明であり，つ
いで図３には図示しない後工程について説明する。 Ｇ：封止 三フッ化塩化エチレン樹脂フイルムに接着剤をコートし
た防湿膜（総厚み２５０μｍ）を所定寸法に切断し，図
３（ｆ）で得られた電極リード７を取り付けた積層体の
上下面に，上記三フッ化塩化エチレン樹脂フイルムの防
湿膜をそれぞれ配し，電磁誘導加熱コイルの間を通過さ
せて，防湿膜を熱圧着シールする。その時の条件は，次
の通りである。 上ロ−ラ温度：１３０℃ 下ロ−ラ温度：１３０〜１５０℃ 線圧力 ： ３０ｋｇ／ｃｍ2 ロ−ラ速度 ： １０ｃｍ／ｍｉｎ Ｈ：性能評価 上記の完成品を定電流測定法を用いて，各パラメータ毎
に輝度を測定する。従来法のガラス基板の上にＩＴＯ及
び発光層等を成膜し，陰極材料にＭｇ−Ａｇ（１０％）
をスパッター装置で成膜したサンプルに比し，低い駆動
電圧で高い相対輝度が得られた。測定結果は，電流密度
５０ｍＡ／ｃｍ2 で約１０００ｃｄ／ｍ2 の輝度であっ
た。D: Peeling of peeling film Next, as shown in FIG. 3 (d), the peeling film 50 is peeled off. In this case, of course, the light emitting layer 2 above it
Are also peeled off together, and the mounting portion of the electrode lead 7 is exposed. E: Cathode transfer Next, although not shown, a transfer member 60 having a thickness of 100 μm is used.
A metal indium for the cathode 1 is formed into a film having a thickness of 3.5 ± 0.5 μm on the support film 60a made of m tetrafluoroethylene resin film by the vacuum deposition method. The peel strength of indium metal at this time is 2.6 ± 0.7 g / 5 m
It was m. Then, as shown in FIG. 3 (e), the surface of the metal indium and the surface of the light emitting layer 2 are aligned with each other and passed between the electromagnetic induction heating coils to melt the metal indium and melt-bond the metal indium. The temperature of metallic indium at the time of transfer is 160 ° C., which is slightly higher than the melting point of metallic indium, 157 ° C. The conditions at that time are as follows. Upper roller temperature: 150 ° C. Lower roller temperature: 150 to 180 ° C. Linear pressure: 30 kg / cm 2 Roller speed: 10 cm / min After melt bonding, the support film 60a on the surface is removed.
The transfer in this step may be either partial transfer or front surface transfer, as long as it is a method that achieves the purpose of display. F: Attaching the electrode lead Next, as shown in FIG. 3 (f), the T-shaped electrode lead 7 together with a fixing tape (not shown) is provided at a predetermined position on the cathode 1 (metal indium) surface and at the above-mentioned FIG. 3 (d). It is attached to each of the exposed electrode attachment portions on the surface of the anode material layer (ITO) described. The above is the description of FIG. 3, and then a post-process not shown in FIG. 3 will be described. G: Encapsulation A layer of laminated fluorotrifluoroethylene resin film coated with an adhesive was cut to a predetermined size with a moisture-proof film (total thickness 250 μm), and the electrode leads 7 obtained in FIG. 3 (f) were attached. The moisture-proof film of the above-mentioned trifluorochloroethylene resin film is arranged on the lower surface, respectively, and the moisture-proof film is thermocompression-bonded by passing it between the electromagnetic induction heating coils. The conditions at that time are as follows. Upper roller temperature: 130 ° C. Lower roller temperature: 130 to 150 ° C. Linear pressure: 30 kg / cm 2 Roller speed: 10 cm / min H: Performance evaluation Using the constant current measurement method for the above finished product, The brightness is measured for each parameter. ITO and light emitting layer are formed on the glass substrate of the conventional method, and Mg-Ag (10%) is used as the cathode material.
High relative brightness was obtained at a low driving voltage compared to the sample formed by sputtering with a sputtering device. The measurement result was a luminance of about 1000 cd / m 2 at a current density of 50 mA / cm 2 .
【００２０】[0020]
【発明の効果】本発明によれば，仕事関数の小さい金属
の薄膜が形成されたフイルムから仕事関数の小さい金属
を加熱溶融させて発光層に転写することにより陰極を形
成しているので，陰極と発光層の接合が良好に行なわ
れ，発光輝度，発光効率の向上が可能となる。また，金
属インジウム等の仕事関数の小さい金属膜が形成された
フイルムは，予め巻き取り蒸着機等で連続的に生産して
おくことにより生産性が向上し，比較的安価に入手可能
であり，素子を形成する際には，真空成膜技術を適用す
ることなく，密着性の良い陰極構成を生産性良く得るこ
とができる。According to the present invention, since a metal having a low work function is heated and melted from a film having a thin film of a metal having a low work function formed thereon and transferred to a light emitting layer, a cathode is formed. The light-emitting layer and the light-emitting layer are joined well, and the light emission brightness and light emission efficiency can be improved. In addition, the film on which a metal film having a small work function such as metallic indium is formed is improved in productivity by continuously producing in advance by a winding vapor deposition machine or the like, and is relatively inexpensively available. When forming an element, a cathode structure with good adhesion can be obtained with good productivity without applying a vacuum film forming technique.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の有機薄膜ＥＬ素子の実施例について，
防湿フイルムの一部を切除して示す模式的な斜視図であ
る。FIG. 1 shows an example of an organic thin film EL device of the present invention,
It is a typical perspective view which cuts off a part of moisture-proof film.
【図２】本発明実施例の工程図である。FIG. 2 is a process drawing of an example of the present invention.
【図３】本発明実施例の要部の工程を模式的に説明する
断面図である。FIG. 3 is a cross-sectional view schematically illustrating a process of a main part of the embodiment of the present invention.
【図４】本発明における発光層の構造モデルの態様を説
明する図である。FIG. 4 is a diagram illustrating an aspect of a structural model of a light emitting layer according to the present invention.
【図５】公知の有機薄膜ＥＬ素子の側面図である。FIG. 5 is a side view of a known organic thin film EL element.
【図６】従来技術の有機薄膜ＥＬ素子の側面図である。FIG. 6 is a side view of a conventional organic thin film EL element.
【図７】従来技術の有機薄膜ＥＬ素子の他の例を示し，
図７（ａ）はその構造の要部を展開して説明する斜視
図，図７（ｂ）はその層構成を説明する模式的な側面図
である。FIG. 7 shows another example of a conventional organic thin film EL device,
FIG. 7 (a) is a perspective view for explaining an expanded main part of the structure, and FIG. 7 (b) is a schematic side view for explaining its layer structure.
１ 陰極 ２ 発光層 ２ａ 有機発光体層 ２ｂ 有機発光体層 ２ｃ 有機発光体層 ３ 正孔注入材料層 ４ 電子注入材料層 ５ 陽極 ５ａ 陽極支持体 ５ｂ 陽極材料層 ６ 集電体 ７ 電極リード ８ 吸湿フイルム ９ 防湿フイルム １０ 固定テープ ５０ 剥離用フイルム ６０ 転写体 ６０ａ 支持体フイルム １０１ 陰極 １０２ 発光層 １０３ 正孔注入層 １０５ 陽極 １１１ 封止枠 １１２ Ｎ2 ガス １１３ ガラスDESCRIPTION OF SYMBOLS 1 cathode 2 light emitting layer 2a organic light emitting layer 2b organic light emitting layer 2c organic light emitting layer 3 hole injection material layer 4 electron injection material layer 5 anode 5a anode support 5b anode material layer 6 current collector 7 electrode lead 8 moisture absorption Film 9 Moisture-proof film 10 Fixing tape 50 Peeling film 60 Transfer body 60a Supporting film 101 Cathode 102 Light emitting layer 103 Hole injection layer 105 Anode 111 Sealing frame 112 N 2 gas 113 Glass
Claims (12)
を注入し，陰極より電子を注入することにより発光させ
る有機薄膜ＥＬ素子であり，前記発光層を陽極及び陰極
で挟み込み，その両側に防湿層を配設した有機薄膜ＥＬ
素子において，陰極として仕事関数の小さい金属膜を前
記発光層上に溶融接着したことを特徴とする有機薄膜Ｅ
Ｌ素子。1. An organic thin film EL device which emits light by injecting holes from an anode and electrons from a cathode into a light emitting layer containing an organic light emitting body, wherein the light emitting layer is sandwiched between an anode and a cathode, and both sides thereof are sandwiched. Organic thin film EL with moisture barrier layer
In the device, an organic thin film E characterized in that a metal film having a small work function as a cathode is melt-bonded onto the light emitting layer.
L element.
て，正孔注入材料層，有機発光体層，電子注入材料層が
順に積層されていることを特徴とする請求項１記載の有
機薄膜ＥＬ素子。2. The organic light emitting device according to claim 1, wherein the light emitting layer comprises a hole injecting material layer, an organic light emitting layer, and an electron injecting material layer which are sequentially stacked from the anode side toward the cathode side. Thin film EL device.
電子注入材料が混合された層であることを特徴とする請
求項１記載の有機薄膜ＥＬ素子。3. The light emitting layer comprises a hole injection material, an organic light emitting material,
The organic thin film EL device according to claim 1, wherein the organic thin film EL device is a layer in which an electron injection material is mixed.
て，正孔注入材料の性質を兼ね備えた有機発光体層と電
子注入材料層とが順に積層されていることを特徴とする
請求項１記載の有機薄膜ＥＬ素子。4. The light emitting layer is characterized in that an organic light emitting layer having the property of a hole injecting material and an electron injecting material layer are sequentially laminated from the anode side to the cathode side. 1. The organic thin film EL device according to 1.
て，正孔注入材料と有機発光体が混合された層と，電子
注入材料層とが順に積層されていることを特徴とする請
求項１記載の有機薄膜ＥＬ素子。5. The light emitting layer is characterized in that a layer in which a hole injection material and an organic light emitting material are mixed and an electron injection material layer are sequentially stacked from the anode side toward the cathode side. Item 2. The organic thin film EL device according to item 1.
て，正孔注入材料層と，電子注入材料の性質を兼ね備え
た有機発光体層とが順に積層されていることを特徴とす
る請求項１記載の有機薄膜ＥＬ素子。6. The light emitting layer is characterized in that a hole injecting material layer and an organic light emitting material layer having a property of an electron injecting material are sequentially laminated from the anode side to the cathode side. Item 2. The organic thin film EL device according to item 1.
て，正孔注入材料層と，有機発光体と電子注入材料が混
合された層とが順に積層されていることを特徴とする請
求項１記載の有機薄膜ＥＬ素子。7. The light emitting layer is characterized in that a hole injection material layer and a layer in which an organic light emitting material and an electron injection material are mixed are sequentially laminated from the anode side to the cathode side. Item 2. The organic thin film EL device according to item 1.
を注入し，陰極より電子を注入することにより発光させ
る有機薄膜ＥＬ素子であり，前記発光層を陽極及び陰極
で挟み込み，その両側に防湿層を配設した有機薄膜ＥＬ
素子の製造方法において，陽極上に発光層を形成する工
程と，支持体フイルム上に設けた仕事関数の小さい金属
膜を前記発光層面に転写して陰極を形成する工程を含む
ことを特徴とする有機薄膜ＥＬ素子の製造方法。8. An organic thin film EL device which emits light by injecting holes from an anode and electrons from a cathode into a light emitting layer containing an organic light emitting body, wherein the light emitting layer is sandwiched between an anode and a cathode, and both sides thereof are sandwiched. Organic thin film EL with moisture barrier layer
A method of manufacturing an element, comprising: a step of forming a light emitting layer on an anode; and a step of forming a cathode by transferring a metal film having a small work function provided on a support film to the surface of the light emitting layer. Method for manufacturing organic thin film EL device.
ウムからなることを特徴とする請求項８記載の有機薄膜
ＥＬ素子の製造方法。9. The method for manufacturing an organic thin film EL element according to claim 8, wherein the metal film having a low work function is made of indium metal.
５μｍで支持体フイルム上に設けられ，純度４Ｎである
ことを特徴とする請求項９記載の有機薄膜ＥＬ素子の製
造方法。10. The metal indium has a film thickness of 3.5 ± 0.
The method for producing an organic thin film EL device according to claim 9, wherein the organic thin film EL device has a thickness of 5 μm and is provided on a support film and has a purity of 4N.
ウムの溶融接着により行われることを特徴とする請求項
９記載の有機薄膜ＥＬ素子の製造方法。11. The method of manufacturing an organic thin film EL element according to claim 9, wherein the transfer of the metal indium is performed by fusion bonding of the metal indium.
ネーター方式で行うことを特徴とする請求項１１記載の
有機薄膜ＥＬ素子の製造方法。12. The method for producing an organic thin film EL element according to claim 11, wherein the fusion bonding of the metal indium is performed by a thermal laminator method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10429594A JP3585524B2 (en) | 1994-04-20 | 1994-04-20 | Manufacturing method of organic thin film EL element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10429594A JP3585524B2 (en) | 1994-04-20 | 1994-04-20 | Manufacturing method of organic thin film EL element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07288185A true JPH07288185A (en) | 1995-10-31 |
| JP3585524B2 JP3585524B2 (en) | 2004-11-04 |
Family
ID=14376942
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10429594A Expired - Fee Related JP3585524B2 (en) | 1994-04-20 | 1994-04-20 | Manufacturing method of organic thin film EL element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11260549A (en) * | 1998-03-09 | 1999-09-24 | Seiko Epson Corp | Manufacture of organic el display device |
| JP2002093586A (en) * | 2000-09-19 | 2002-03-29 | Semiconductor Energy Lab Co Ltd | Luminescence equipment and its producing method |
| JP2002208478A (en) * | 2000-12-23 | 2002-07-26 | Lg Philips Lcd Co Ltd | Electroluminescent element |
| JP2004503066A (en) * | 2000-07-12 | 2004-01-29 | スリーエム イノベイティブ プロパティズ カンパニー | Encapsulated organic electronic device and method of manufacturing the same |
| JP2004506985A (en) * | 2000-08-18 | 2004-03-04 | シーメンス アクチエンゲゼルシヤフト | Encapsulated organic electronic component, method of manufacture and use thereof |
| WO2004066332A2 (en) * | 2003-01-21 | 2004-08-05 | Osram Opto Semiconductors Gmbh | Cathode for an organic electronics component |
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| US7854640B2 (en) | 2000-08-04 | 2010-12-21 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and manufacturing method therefor |
| JP2013225279A (en) * | 2012-04-19 | 2013-10-31 | Samsung Electro-Mechanics Co Ltd | Touch panel and method for manufacturing the same |
| JP2014026853A (en) * | 2012-07-27 | 2014-02-06 | Konica Minolta Inc | Organic electroluminescent element and sealing method of organic electroluminescent panel |
| CN103921496A (en) * | 2013-01-10 | 2014-07-16 | 海洋王照明科技股份有限公司 | Conductive thin film, preparation method and application thereof |
| JP2016091710A (en) * | 2014-10-31 | 2016-05-23 | コニカミノルタ株式会社 | Surface light-emitting module |
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| JPH11260549A (en) * | 1998-03-09 | 1999-09-24 | Seiko Epson Corp | Manufacture of organic el display device |
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| US7854640B2 (en) | 2000-08-04 | 2010-12-21 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and manufacturing method therefor |
| JP2004506985A (en) * | 2000-08-18 | 2004-03-04 | シーメンス アクチエンゲゼルシヤフト | Encapsulated organic electronic component, method of manufacture and use thereof |
| JP2002093586A (en) * | 2000-09-19 | 2002-03-29 | Semiconductor Energy Lab Co Ltd | Luminescence equipment and its producing method |
| US7495390B2 (en) | 2000-12-23 | 2009-02-24 | Lg Display Co., Ltd. | Electro-luminescence device with improved thermal conductivity |
| JP2002208478A (en) * | 2000-12-23 | 2002-07-26 | Lg Philips Lcd Co Ltd | Electroluminescent element |
| WO2004066332A2 (en) * | 2003-01-21 | 2004-08-05 | Osram Opto Semiconductors Gmbh | Cathode for an organic electronics component |
| WO2004066332A3 (en) * | 2003-01-21 | 2005-01-27 | Osram Opto Semiconductors Gmbh | Cathode for an organic electronics component |
| JP2005285732A (en) * | 2003-12-16 | 2005-10-13 | Dainippon Printing Co Ltd | Organic functional element and its manufacturing method |
| JP2006216563A (en) * | 2005-02-04 | 2006-08-17 | Samsung Sdi Co Ltd | Method of manufacturing organic electroluminescent element |
| JP2005158757A (en) * | 2005-03-07 | 2005-06-16 | Seiko Epson Corp | Process of manufacture of organic electroluminescent display device |
| JP4548153B2 (en) * | 2005-03-07 | 2010-09-22 | セイコーエプソン株式会社 | Manufacturing method of organic EL display device |
| JP2008535177A (en) * | 2005-03-31 | 2008-08-28 | ゼネラル・エレクトリック・カンパニイ | Organic electronic devices having an external barrier layer |
| WO2010113727A1 (en) * | 2009-03-31 | 2010-10-07 | ブラザー工業株式会社 | Organic el element and manufacturing method therefor |
| JP2010238479A (en) * | 2009-03-31 | 2010-10-21 | Brother Ind Ltd | Organic el element and manufacturing method of organic el element |
| JP2013225279A (en) * | 2012-04-19 | 2013-10-31 | Samsung Electro-Mechanics Co Ltd | Touch panel and method for manufacturing the same |
| JP2014026853A (en) * | 2012-07-27 | 2014-02-06 | Konica Minolta Inc | Organic electroluminescent element and sealing method of organic electroluminescent panel |
| CN103921496A (en) * | 2013-01-10 | 2014-07-16 | 海洋王照明科技股份有限公司 | Conductive thin film, preparation method and application thereof |
| JP2016091710A (en) * | 2014-10-31 | 2016-05-23 | コニカミノルタ株式会社 | Surface light-emitting module |
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