JPH07153571A - Organic thin film el element - Google Patents

Organic thin film el element

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Publication number
JPH07153571A
JPH07153571A JP5319270A JP31927093A JPH07153571A JP H07153571 A JPH07153571 A JP H07153571A JP 5319270 A JP5319270 A JP 5319270A JP 31927093 A JP31927093 A JP 31927093A JP H07153571 A JPH07153571 A JP H07153571A
Authority
JP
Japan
Prior art keywords
light emitting
layer
thin film
organic thin
emitting 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
Application number
JP5319270A
Other languages
Japanese (ja)
Other versions
JP3254570B2 (en
Inventor
Makoto Takahashi
真 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
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  • Electroluminescent Light Sources (AREA)

Abstract

PURPOSE:To improve productivity, reduce cost, and provide a thin light source, a lightweight light source and a free-shaped light source. CONSTITUTION:An organic thin film EL element is formed in such a way that a material where an Au current collecting body 6 having a large work function is arranged on an ITO layer of a positive electrode 5 is arranged on one side of a light emitting layer 2 (a light emitting layer formed by mixing an electron hole implanting material, an organic light emitting body and an electron implanting material together), and a material where an electrode material layer (an allay layer which has a small work function and is formed of Mg and Ag) is arranged on an Al board of a negative electrode 1 is arranged on the opposite side of the light emitting layer 2, and the upper and lower parts are sandwiched by moisture absorptive films 8 and 8, and the further upper and lower parts are sandwiched by moisture-proof films 9 and 9, and the whole bodies are lastly laminated on each other.

Description

【発明の詳細な説明】Detailed Description of the Invention

【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6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】[0003]

【発明が解決しようとする課題】本発明は,上記の問題
点を解決し,生産性,コスト,薄型光源,軽重量光源,
自由形状の光源を得ることを課題とする。
SUMMARY OF THE INVENTION The present invention solves the above problems and improves productivity, cost, thin light source, light weight light source,
The subject is to obtain a free-form light source.

【0004】[0004]

【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素子において,前記発光層を陽極材料層及び陰
極材料層で挟み込み,その両側に吸湿層,防湿層を配設
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,陰極が,アルミ箔の表面に,仕事
関数の小さい金属またはその合金を,発光層と接する面
に配したもの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9記載の手段
は,仕事関数の小さい金属またはその合金が,Mg膜,
Mg:Agの合金または積層膜,Mg:Inの合金また
は積層膜であることを特徴とする請求項8記載の有機薄
膜EL素子である。本発明の請求項10記載の手段は,
陽極の内側に仕事関数の大きい集電体を配したことを特
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11記載の手段は,仕事関数の大きい集電体
がAu,Te,Pt,Se,CuI,から選ばれた材料
であることを特徴とする請求項10記載の有機薄膜EL
素子である。本発明の請求項12記載の手段は,集電体
の形状が線状,L字状,□型状から選ばれた形状である
ことを特徴とする請求項10又は請求項11記載の有機
薄膜EL素子である。本発明の請求項13記載の手段
は,防湿層がポリエステル樹脂フイルム上に水分の透湿
防止用バリヤー層を設けたもの又は三フッ化塩化エチレ
ン樹脂フイルムにより形成された請求項1記載の有機薄
膜EL素子である。
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. 2. In the organic thin film EL device, the light emitting layer is sandwiched between an anode material layer and a cathode material layer, and a moisture absorbing layer and a moisture proof layer are provided on both sides of the light emitting layer. 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. Claim 1
It is the described organic thin film EL device. 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, from the anode side toward the cathode side,
2. The organic thin film EL device according to claim 1, wherein an organic light emitting layer having a property of a hole injecting material and an electron injecting material layer are sequentially stacked. Claim 5 of the present invention
The means described is characterized in that the light emitting layer comprises a layer in which a hole injection material and an organic light emitting material are mixed and an electron injection material layer, which are sequentially stacked from the anode side toward the cathode side. Item 2. The organic thin film EL device according to item 1. 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 characterized in that the cathode is one in which a metal having a low work function or an alloy thereof is disposed on the surface of an aluminum foil on the surface in contact with the light emitting layer. Is an organic thin film EL device. According to a ninth aspect of the present invention, in which a metal having a small work function or an alloy thereof is a Mg film,
9. The organic thin film EL element according to claim 8, wherein the organic thin film EL element is an alloy or laminated film of Mg: Ag or an alloy or laminated film of Mg: In. The means according to claim 10 of the present invention is
2. The organic thin film EL device according to claim 1, wherein a current collector having a large work function is arranged inside the anode. According to the eleventh aspect of the present invention, the current collector having a large work function is a material selected from Au, Te, Pt, Se and CuI, and the organic thin film EL according to the tenth aspect.
It is an element. The means according to claim 12 of the present invention is characterized in that the shape of the current collector is a shape selected from a linear shape, an L shape and a □ shape, and the organic thin film according to claim 10 or 11. It is an EL element. According to a thirteenth aspect of the present invention, the moisture-proof layer comprises a polyester resin film provided with a barrier layer for preventing moisture permeation of moisture, or an organic thin film according to the first aspect of the present invention. It is an EL element.

【0005】以下,従来の図6の有機薄膜EL素子と対
比させて,図3に,本発明の有機薄膜EL素子の構造の
要部を展開した斜視図として示す。(これは,後記する
図4(c)の発光層の構成に対応する)有機発光体層2
cと正孔注入材料層3とを積層して発光層とし,正孔注
入材料層3側に陽極5を配し,有機発光体層2c側に陰
極1を配する。その上下を吸湿フイルム8,8で挟み,
さらに,その上下を防湿フイルム9,9で挟み,最後に
全体をラミネートして形成されている。上記の構成は,
従来技術との比較で説明したが,実際に,パネル化する
ときは有機発光体層2cと正孔注入材料層3の材料と結
合剤とを混ぜて,パネル化することが望ましい。結合剤
は,パネル化の方法によっては,使わなくてもよい。
Hereinafter, in contrast to the conventional organic thin film EL element shown in FIG. 6, FIG. 3 shows an exploded perspective view of the essential part of the structure of the organic thin film EL element of the present invention. (This corresponds to the structure of the light emitting layer of FIG. 4C described later) Organic light emitting layer 2
c and the hole injection material layer 3 are laminated to form a light emitting layer, the anode 5 is arranged on the hole injection material layer 3 side, and the cathode 1 is arranged on the organic light emitting layer 2c side. The upper and lower sides are sandwiched between the moisture absorbing films 8 and 8,
Further, it is formed by sandwiching the upper and lower sides with moisture-proof films 9, 9 and finally laminating the whole. The above configuration is
As described in comparison with the prior art, when it is actually formed into a panel, it is desirable to mix the material of the organic light emitting layer 2c and the hole injection material layer 3 with a binder to form a panel. The binder may not be used depending on the paneling method.

【0006】次に,本発明の構成要素の態様について説
明する。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しめすように,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。
Next, aspects of the constituent elements of the present invention will be described. 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.
Is the standard, and FIG. 4 (a) and FIG. 4 (c) 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 composed of a hole injection material layer 3, an organic light emitting layer 2b, and an electron injection material layer 4 in this order from the anode 5 side. 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 of (c) is shown in FIG.
Each of the layers is composed of a material having the properties of both an organic light emitting material and an electron injection material. Further, in order to improve the light emission efficiency, a hole barrier layer, an electron barrier layer, etc. are interposed 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, respectively. It may have a different structure. Further, the organic light emitting layer 2a shown in FIG. 4 (a) may be formed by mixing an organic light emitting body and a hole injection material, and the organic light emitting layer 2c shown in FIG. You may comprise by mixing an organic light emitting body and an electron injection material. In addition, the light emitting layer is composed of an organic light emitting material, a hole injection material,
If the electron injection material is formed as a bulk single layer in which it is uniformly mixed, it is easy to form a panel and is advantageous in improving durability. Furthermore, it becomes a panel, and more
In order to approach the practical level, hole injection materials, organic light-emitting materials, electron injection materials, etc. are materials that do not generate sufficient molecular strain,
In other words, the cathode is made of a material having a small interaction of molecular substituents, the cathode is made of a material having a small work function and is not easily oxidized, and further, the material is not deteriorated thermally and electrically, The selected material is desirable. In addition, the organic thin film EL element of the present invention can be obtained by collecting water in the panel and preventing water from entering from the outside to form a panel, and the range of use thereof is further expanded.

【0007】以下,本発明の有機薄膜EL素子の各部に
ついて説明する。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。
Each part of the organic thin film EL element of the present invention will be described below. 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.

【0008】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.

【0009】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 injection material has a function of transmitting the electrons injected from the cathode to the organic light-emitting body, and by placing this layer between the cathode and the organic light-emitting body 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.

【0010】本発明の有機薄膜EL素子の発光機構は,
注入発光タイプである。比較の意味で述べると,無機薄
膜EL素子及び粉末分散型EL素子は,電界発光タイプ
である。従って,注入発光タイプは電極から電荷を注入
するので,電極の材料選択が難しい。言い換えると,陽
極は,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,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,S
nO2 ,ITO,Pt,Se,Te等である。更に,光
透過率の良いものが使われ,ITOが普通一般的に使わ
れる。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,Na,Na−K,Li,Mg,C
a等の I,II族 化合物, Ga,InのIII 族金属
(B,Alを除く)が最適である。一般的には,Mgが
広く用いることができ,Mg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。Inについても同様な効果があり,MgにI
nを添加したものは,劣化が遅い。また,MgにAgを
積層したもの,MgにInを積層したものも使用するこ
とができる。この場合に,AgあるいはInの層が発光
層と接触するようにしても,仕事関数が小さいため問題
はない。
The light emitting mechanism of the organic thin film EL device of the present invention is as follows.
It is an injection light emitting type. In terms of comparison, the inorganic thin film EL element and the powder dispersion type EL element are electroluminescence type. Therefore, in the injection emission type, electric charge is injected from the electrode, and it is difficult to select the material of the electrode. In other words, the anode is an electrically conductive compound of a metal having a high work function or an alloy thereof, and a material having a high ionization potential and a low electron affinity is optimal. For example, Au, CuI, S
nO 2 , ITO, Pt, Se, Te and the like. Further, a material having a good light transmittance is used, and ITO is generally commonly used. The cathode is a metal with a small work function (4.
(0 eV or less) or an electrically conductive compound of its alloy, which has a small ionization potential and a large electron affinity is used. For example, Na, Na-K, Li, Mg, C
Group I compounds such as a and group III metals of Ga and In (excluding B and Al) are most suitable. In general, Mg can be widely used, and oxidation is fast only with Mg.
A material is used in which Ag or Cu is added in an amount of 3 to 15% to prevent oxidation from progressing. The optimum amount of addition is 5-10
%. In has the same effect, and I
The one to which n is added deteriorates slowly. Further, it is also possible to use a laminate of Ag on Mg and a laminate of In on Mg. In this case, even if the Ag or In layer comes into contact with the light emitting layer, there is no problem because the work function is small.

【0011】集電体は,陽極5から有機発光体層(2
a,2b,2c)に正孔を注入しやすくするために陽極
5の上に形成する。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,図5に示すよう
に,発光面積が小さい場合には,図5(a)のような線
状の集電体6を,発光面積が中程度の場合には,図5
(b)のようなL字状の集電体6を,発光面積が大きい
場合には,図5(c)のような□型状の集電体6を配設
する。集電体6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。
The current collector is composed of the anode 5 to the organic light emitting layer (2
It is formed on the anode 5 in order to facilitate the injection of holes into a, 2b, 2c). When forming the current collector, it depends on the area of the panel, but typically, as shown in FIG. 5, when the light emitting area is small, a linear current collector as shown in FIG. When the light emitting area of the body 6 is medium,
When the light emitting area is large, the L-shaped current collector 6 as shown in FIG. 5B is provided as the □ -shaped current collector 6 as shown in FIG. 5C. As a material of the current collector 6, CuI is used in addition to a 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.

【0012】吸湿層は,パッケージングされたときの水
分を除去する役目を持つ。通常使用するものは,ナイロ
ン6フイルムが用いられる。
The moisture absorption layer has a function of removing moisture when packaged. Nylon 6 film is usually used.

【0013】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 invasion of moisture from the outside, and is usually a barrier layer that does not allow moisture to pass on a 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.

【0014】[0014]

〔陰極の形成〕[Formation of cathode]

(1)Al基板 厚み70μm(硬質),純度99.9
%のものを使用する。 (2)陰極1の形成 形成条件(スパッタリング法) DCスパッタリング装置 ターゲット 組成比 Mg:Ag=9〜10:1 純度99.99% ガス出し 180℃ 基板温度 100℃ スパッタガス圧 3×10-3Torr スパッタ電流 1A 背圧 3×10-7Torr スパッタガス Ar(30SCCM) 予め,表面を軽く逆スパッタリングしておき,上記の条
件で専用マスクを使って,50〜70nmの膜形成を行
う。 (3)切断 上記の(2)で膜形成したものを,使用の
大きさに切断する。 〔発光層の形成〕 (4)材料秤量 A;材料 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 B;結合剤 ポリカーボネート樹脂 50.00重量部 1,2−ジクロロエタン 50.00重量部 (5)混合 ホモジナイザーのカップに(4)の材料Aを20g入れ
て,2500rpmで混合し,つぎに,(4)の材料B
を20gを追加し,2500rpmで混合する。(混合
比 A:B=1:1) (6)塗布 所定サイズのAl基板の上に,(1)〜(3)で形成し
たMg:Ag=10:1の膜を形成した陰極1上に上記
の混合ペーストを数cc滴下し,スピンナで3500r
pmで20sec間回転して塗布し,膜厚を40〜70
nmとした。 (7)乾燥 120℃,30minで乾燥し,その後冷
却する。 (8)電極リード7 T字型リードを作成する。 (9)リード付 (8)の電極リード7を固定テープと共にAl基板の裏
面側に固定する。 〔陽極の形成〕 (10)陽極5 70μmのポリエステル樹脂フイルム上に,シート抵抗
100Ω/□のITOを形成したものを使用する。光透
過率は85〜90%である。 (11)集電体6の形成 膜形成条件:上記(10)のITO付きフイルムの内側
に,Auにより集電体6を形成する。 DCスパッタリング装置 ターゲット Au 純度99.999% ガス出し 150℃ 基板温度 室温 スパッタガス圧 3×10-3Torr スパッタガス Ar(35SCCM) スパッタ電流 1A (12)切断 上記の(11)で膜形成した陽極5を使用の大きさに切
断する。 (13)電極リード7 上記(8)と同じ。 (14)リード付 固定テープで電極リード7を所定の
位置に取り付ける。 〔封止〕 (15)吸湿フイルム8 厚み100μmのナイロン6
フイルムを使用する。 (16)切断 カッタで吸湿フイルム8を所定の寸法に
切断する。 (17)防湿フイルム9 三フッ化塩化エチレン樹脂フイルムに熱賦活性接着剤を
コートした厚み250μm,透湿率40mg/m2 以下
のものを使用する。 (18)切断 カッタで防湿フイルム9を所定の寸法に
切断する。 (19)乾燥 発光層2を塗布した陰極1,集電体6を形成した陽極
5,切断した吸湿フイルム8,切断した防湿フイルム9
を90℃,約1時間の乾燥を行う。 (20)重ね合わせ 乾燥終了後,すばやく乾燥炉から取り出し,発光層2を
塗布した陰極1の上に,陽極5の集電体6が形成してあ
る面を内側にして重ね合わせ,次に,切断した吸湿フイ
ルム8を上下に合わせ,最後に防湿フイルム9をその上
下に重ね合わせる。 (21)熱圧着 前工程で重ね合わせたフイルムコンポーネントを,電磁
誘導加熱コイルの間を通過させて,防湿フイルム9に塗
布してある接着剤を溶かして熱圧着する。 熱圧着(ラミネート)条件 上ロ−ラ温度 130℃ 下ロ−ラ温度 130〜150℃ 線圧力 30kg/cm2 ロ−ラ速度 10cm/min (22)性能検査 定電流測定法を使って,各パラメー
タ毎に輝度を測定する。
(1) Al substrate 70 μm thick (hard), purity 99.9
Use the% one. (2) Formation of cathode 1 Formation conditions (sputtering method) DC sputtering device target Composition ratio Mg: Ag = 9 to 10: 1 Purity 99.99% Outgassing 180 ° C. Substrate temperature 100 ° C. Sputtering gas pressure 3 × 10 −3 Torr Sputtering current 1 A Back pressure 3 × 10 −7 Torr Sputtering gas Ar (30 SCCM) The surface is lightly reverse-sputtered beforehand, and a film of 50 to 70 nm is formed under the above conditions using a dedicated mask. (3) Cutting The film formed in (2) above is cut into a size for use. [Formation of Light-Emitting Layer] (4) Material Weighing A; Material 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 light-emitting body) 1,2 dichloroethane 50.00 parts by weight B; Binder Polycarbonate resin 50.00 parts by weight 1,2-dichloroethane 50.00 parts by weight (5) Mixing 20 g of the material A of (4) in a homogenizer cup. Put it in, mix it at 2500 rpm, and then material B of (4)
20 g and mix at 2500 rpm. (Mixing ratio A: B = 1: 1) (6) Coating On the cathode 1 on which the film of Mg: Ag = 10: 1 formed in (1) to (3) is formed on the Al substrate of a predetermined size. Add several cc of the above mixed paste and spinner at 3500r
Rotate at pm for 20 seconds and apply to a film thickness of 40-70
nm. (7) Drying Dry at 120 ° C. for 30 minutes and then cool. (8) Electrode lead 7 A T-shaped lead is prepared. (9) With lead The electrode lead 7 of (8) is fixed to the back side of the Al substrate together with the fixing tape. [Formation of Anode] (10) Anode 5 A 70 μm polyester resin film on which ITO having a sheet resistance of 100 Ω / □ is formed is used. The light transmittance is 85 to 90%. (11) Formation of Current Collector 6 Film forming condition: The current collector 6 is formed of Au inside the film with ITO of the above (10). DC sputtering device Target Au Purity 99.999% Gas out 150 ° C. Substrate temperature Room temperature Sputtering gas pressure 3 × 10 −3 Torr Sputtering gas Ar (35SCCM) Sputtering current 1A (12) Cutting Anode 5 formed by the above (11) Cut to size of use. (13) Electrode lead 7 Same as (8) above. (14) With lead Attach the electrode lead 7 at a predetermined position with a fixing tape. [Sealing] (15) Moisture absorbing film 8 Nylon 6 having a thickness of 100 μm
Use the film. (16) Cutting The moisture absorbing film 8 is cut into a predetermined size with a cutter. (17) Moisture-proof film 9 A trifluorochloroethylene resin film coated with a heat-activatable adhesive is used, and the thickness is 250 μm and the moisture permeability is 40 mg / m 2 or less. (18) Cutting The moisture-proof film 9 is cut into a predetermined size with a cutter. (19) Drying The cathode coated with the light emitting layer 2, the anode formed with the current collector 6, the cut moisture-absorbing film 8, and the cut moisture-proof film 9
Is dried at 90 ° C. for about 1 hour. (20) Superposition After completion of drying, the stack is quickly taken out of the drying oven and superposed on the cathode 1 coated with the light emitting layer 2 with the surface of the anode 5 on which the current collector 6 is formed facing inward. The cut moisture-absorbing film 8 is put on top and bottom, and finally the moisture-proof film 9 is put on top of it. (21) Thermocompression bonding The film components laminated in the previous step are passed between the electromagnetic induction heating coils, and the adhesive applied to the moisture-proof film 9 is melted and thermocompression bonded. Thermo-compression (lamination) conditions Upper roller temperature 130 ° C Lower roller temperature 130-150 ° C Line pressure 30kg / cm 2 Roller speed 10cm / min (22) Performance inspection Each parameter using constant current measurement method. Measure the brightness every time.

【0015】上記の構造でパネル化を実施したときの性
能として,電流密度10mA/cm2 において,本発
明の有機薄膜EL素子と,従来の有機薄膜EL素子と
して,図7に示すように,ガラス基板上に,陽極として
ITO膜,正孔注入材料層としてポリ(N−ビニルカル
バゾール)膜,有機発光体層としてクマリン膜,電子注
入材料層としてペリレン膜,陰極としてMg:Ag膜
を,順に真空蒸着法により形成したものの,初期輝度及
び500時間経過後の輝度とを対比した結果を表1に示
す。
As a performance when a panel is formed with the above structure, as an organic thin film EL element of the present invention and a conventional organic thin film EL element at a current density of 10 mA / cm 2 , as shown in FIG. On the substrate, an ITO film as an anode, a poly (N-vinylcarbazole) film as a hole injecting material layer, a coumarin film as an organic light emitting layer, a perylene film as an electron injecting material layer, and a Mg: Ag film as a cathode are sequentially vacuumed. Table 1 shows the results of comparison between the initial luminance and the luminance after 500 hours, although they were formed by the vapor deposition method.

【表1】 電流密度10mA/cm2 ,輝度単位:cd/m2 ここで単純に初期輝度を比較した場合,の従来の有機
薄膜EL素子が初期輝度は高いが,長期安定性はの本
発明の実施例が良く,実用性に優れている。
[Table 1] Current density of 10 mA / cm 2 , luminance unit: cd / m 2 Here, when the initial luminance is simply compared, the conventional organic thin film EL element of has a high initial luminance, but the embodiment of the present invention has a long-term stability. Good and practical.

【0016】[0016]

【発明の効果】以上のように,本発明によれば,以下の
ような生産性,コスト,薄型光源,軽重量光源,自由形
状の光源等の効果が得られる。更に,具体的に説明すれ
ば, 生産性向上及び低コスト化 従来の有機薄膜EL素子の発光層の製造に必要であった
真空成膜技術を用いないで,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,L
B法等を適用できるので,設備投資が少なくてすみ,製
造工程も容易である。その結果として,低コスト化が達
成でき,その使用範囲の可能性が拡大し,各種のニーズ
に対応できる。 均一な面光源 従来の光源のように,反射,拡散の対策が不要であり,
モジュールに組み込んだ時,よりその効果が大きく現れ
る。 薄型光源 フイルムを使っているため,総膜厚は1.0mm以下に
設定でき,同様モジュールに組み込んだ時,よりその
効果が大きく現れる。 軽い光源 フイルムを使っているため,重量が軽くなり,同様
モジュールに組み込んだ時,よりその効果が大きく現れ
る。 形状の自由度が大きい 構成材料にフイルムを使っているため,形状の加工がや
りやすい。 専用駆動電源が不要 従来の光源のように,専用の電源を必要とせず,発光面
積によっては乾電池1本で駆動できる。
As described above, according to the present invention, the following effects of productivity, cost, thin light source, light weight light source, free-form light source, etc. can be obtained. More specifically, productivity improvement and cost reduction can be achieved by using a spray method, a spinner method, or a vacuum method, which does not require the vacuum film forming technique which is necessary for manufacturing a light emitting layer of a conventional organic thin film EL element.
Immersion coating method, screen printing method, roll coater method, L
Since the method B can be applied, the equipment investment is small and the manufacturing process is easy. As a result, cost reduction can be achieved, the possibility of its use range expands, and various needs can be met. Uniform surface light source Unlike conventional light sources, no countermeasures for reflection and diffusion are required,
When incorporated into a module, its effect is even more pronounced. Since a thin light source film is used, the total film thickness can be set to 1.0 mm or less, and the effect is more significant when incorporated into a module. Since a light source film is used, the weight is lighter, and the effect is even more pronounced when incorporated into a module. Large degree of freedom in shape Since film is used for the constituent materials, shape processing is easy. No need for a dedicated drive power source Unlike the conventional light source, a dedicated power source is not required, and it can be driven by a single dry cell depending on the light emitting area.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の有機薄膜EL素子の実施例を示し,図
1(a)はその構造の要部を展開して説明する斜視図,
図1(b)はその層構成を説明する模式的な側面図であ
る。
FIG. 1 shows an embodiment of an organic thin film EL element of the present invention, and FIG. 1 (a) is a perspective view for explaining an expanded main part of the structure,
FIG. 1B is a schematic side view illustrating the layer structure.

【図2】本発明の実施例(図1)の製造工程を説明する
ブロック図である。
FIG. 2 is a block diagram illustrating a manufacturing process of the embodiment (FIG. 1) of the present invention.

【図3】本発明の別の態様の有機薄膜EL素子の構造の
要部を展開して説明する斜視図である。
FIG. 3 is a perspective view for developing and explaining a main part of the structure of the organic thin film EL element of another 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】本発明の集電体の態様を説明する模式平面図で
ある。
FIG. 5 is a schematic plan view illustrating an aspect of a current collector of the present invention.

【図6】従来法による有機薄膜EL素子の側面図であ
る。
FIG. 6 is a side view of an organic thin film EL element according to a conventional method.

【図7】従来法による比較例の有機薄膜EL素子の側面
図である。
FIG. 7 is a side view of an organic thin film EL element of a comparative example according to a conventional method.

【符号の説明】[Explanation of symbols]

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 6 集電体 7 電極リード 8 吸湿フイルム 9 防湿フイルム 101 陰極 102c 発光層 103 正孔注入層 105 陽極 111 封止枠 112 N2 ガス 113 ガラス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 6 Current Collector 7 Electrode Lead 8 Moisture Absorption Film 9 Moisture-Proof Film 101 Cathode 102c Light Emission Layer 103 Hole injection layer 105 Anode 111 Sealing frame 112 N 2 gas 113 Glass

Claims (13)

【特許請求の範囲】[Claims] 【請求項1】 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素子において,前記発光層を陽極材料層
及び陰極材料層で挟み込み,その両側に吸湿層,防湿層
を配設したことを特徴とする有機薄膜EL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 material, wherein the light emitting layer is sandwiched between an anode material layer and a cathode material layer. An organic thin film EL device having a moisture absorption layer and a moisture prevention layer on both sides thereof.
【請求項2】 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。
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.
【請求項3】 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。
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.
【請求項4】 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。
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.
【請求項5】 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。
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.
【請求項6】 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。
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.
【請求項7】 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。
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.
【請求項8】 陰極が,アルミ箔の表面に,仕事関数の
小さい金属またはその合金を,発光層と接する面に配し
たもの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。
8. The organic thin-film EL device according to claim 1, wherein the cathode is formed by disposing a metal having a low work function or an alloy thereof on the surface of an aluminum foil on the surface in contact with the light emitting layer.
【請求項9】 仕事関数の小さい金属またはその合金
が,Mg膜,Mg:Agの合金または積層膜,Mg:I
nの合金または積層膜であることを特徴とする請求項8
記載の有機薄膜EL素子。
9. A metal having a low work function or an alloy thereof is a Mg film, an alloy of Mg: Ag or a laminated film, and Mg: I.
9. An alloy of n or a laminated film.
The organic thin film EL device described.
【請求項10】 陽極の内側に仕事関数の大きい集電体
を配したことを特徴とする請求項1記載の有機薄膜EL
素子。
10. The organic thin film EL according to claim 1, wherein a current collector having a large work function is arranged inside the anode.
element.
【請求項11】 仕事関数の大きい集電体がAu,T
e,Pt,Se,CuI,から選ばれた材料であること
を特徴とする請求項10記載の有機薄膜EL素子。
11. A collector having a large work function is Au, T
The organic thin film EL element according to claim 10, wherein the organic thin film EL element is a material selected from e, Pt, Se, and CuI.
【請求項12】 集電体の形状が線状,L字状,□型状
から選ばれた形状であることを特徴とする請求項10又
は請求項11記載の有機薄膜EL素子。
12. The organic thin film EL element according to claim 10 or 11, wherein the shape of the current collector is a shape selected from linear, L-shaped, and □ -shaped.
【請求項13】 防湿層がポリエステル樹脂フイルム上
に水分の透湿防止用バリヤー層を設けたもの又は三フッ
化塩化エチレン樹脂フイルムにより形成された請求項1
記載の有機薄膜EL素子。
13. The moisture-proof layer is formed of a polyester resin film provided with a barrier layer for preventing moisture permeation of moisture, or a trifluorochloroethylene resin film.
The organic thin film EL device described.
JP31927093A 1993-11-26 1993-11-26 Organic thin film EL device Ceased JP3254570B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP31927093A JP3254570B2 (en) 1993-11-26 1993-11-26 Organic thin film EL device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP31927093A JP3254570B2 (en) 1993-11-26 1993-11-26 Organic thin film EL device

Publications (2)

Publication Number Publication Date
JPH07153571A true JPH07153571A (en) 1995-06-16
JP3254570B2 JP3254570B2 (en) 2002-02-12

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Country Link
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