JP3334408B2 - Organic electroluminescent device and method of manufacturing the same - Google Patents
Organic electroluminescent device and method of manufacturing the sameInfo
- Publication number
- JP3334408B2 JP3334408B2 JP4209695A JP4209695A JP3334408B2 JP 3334408 B2 JP3334408 B2 JP 3334408B2 JP 4209695 A JP4209695 A JP 4209695A JP 4209695 A JP4209695 A JP 4209695A JP 3334408 B2 JP3334408 B2 JP 3334408B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- organic electroluminescent
- electroluminescent device
- cathode
- anode
- 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.)
- Expired - Lifetime
Links
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- 238000000206 photolithography Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000005255 pyrrolopyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical class C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- XDDVRYDDMGRFAZ-UHFFFAOYSA-N thiobenzophenone Chemical class C=1C=CC=CC=1C(=S)C1=CC=CC=C1 XDDVRYDDMGRFAZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- 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
- H10K59/873—Encapsulations
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機電界発光素子及びそ
の製造方法に関するものであり、詳しくは、有機化合物
から成る発光層に電界をかけて光を放出する薄膜型デバ
イスの封止方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device and a method of manufacturing the same, and more particularly, to a method of sealing a thin film device which emits light by applying an electric field to a light emitting layer made of an organic compound. It is.
【０００２】[0002]
【従来の技術】従来、薄膜型の電界発光（ＥＬ）素子と
しては、無機材料の〓−〓族化合物半導体であるＺｎ
Ｓ、ＣａＳ、ＳｒＳ等に、発光中心であるＭｎや希土類
元素（Ｅｕ、Ｃｅ、Ｔｂ、Ｓｍ等）をドープしたものが
一般的であるが、上記の無機材料から作製したＥＬ素子
は、 １）交流駆動が必要（５０〜１０００Ｈｚ）、 ２）駆動電圧が高い（〜２００Ｖ）、 ３）フルカラー化が困難（特に青色が問題）、 ４）周辺駆動回路のコストが高い、 という問題点を有している。2. Description of the Related Art Conventionally, as a thin film type electroluminescent (EL) element, Zn, which is an inorganic 〓-〓 compound semiconductor, is used.
In general, S, CaS, SrS, and the like are doped with Mn or a rare earth element (Eu, Ce, Tb, Sm, or the like) which is a luminescence center. However, EL devices manufactured from the above inorganic materials include: 1) AC drive is required (50-1000 Hz), 2) High drive voltage (up to 200 V), 3) It is difficult to achieve full color (especially blue), 4) Cost of peripheral drive circuit is high. ing.
【０００３】しかし、近年、上記問題点の改良のため、
有機薄膜を用いたＥＬ素子の開発が行われるようになっ
た。特に、発光効率を高めるため、電極からのキャリア
ー注入の効率向上を目的として電極の種類の最適化を行
い、芳香族ジアミンから成る有機正孔輸送層と８−ヒド
ロキシキノリンのアルミニウム錯体から成る有機発光層
とを設けた有機電界発光素子の開発（Ａｐｐｌ．Ｐｈｙ
ｓ．Ｌｅｔｔ．，５１巻，９１３頁，１９８７年）によ
り、従来のアントラセン等の単結晶を用いたＥＬ素子と
比較して発光効率の大幅な改善がなされ、実用特性に近
づいている。However, in recent years, in order to improve the above problems,
Development of EL devices using organic thin films has been started. In particular, in order to enhance the luminous efficiency, the type of the electrode is optimized for the purpose of improving the efficiency of carrier injection from the electrode, and the organic luminescent layer composed of an organic hole transport layer composed of an aromatic diamine and the aluminum complex of 8-hydroxyquinoline is used. Of an organic electroluminescent device provided with a layer (Appl. Phys.
s. Lett. , Vol. 51, p. 913, 1987), the luminous efficiency is greatly improved as compared with a conventional EL device using a single crystal such as anthracene, and the practical characteristics are approached.
【０００４】上記の様な低分子材料を用いた電界発光素
子の他にも、有機発光層の材料として、ポリ（ｐ−フェ
ニレンビニレン）（Ｎａｔｕｒｅ，３４７巻，５３９
頁，１９９０年他）、ポリ［２−メトキシ−５−（２−
エチルヘキシルオキシ）−１，４−フェニレンビニレ
ン］（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５８巻，１９
８２頁他）、ポリ（３−アルキルチオフェン）（Ｊｐ
ｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ，３０巻，Ｌ１９３８頁
他）等の高分子材料を用いた電界発光素子の開発や、ポ
リビニルカルバゾール等の高分子に低分子の発光材料と
電子移動材料を混合した素子（応用物理，６１巻，１０
４４頁，１９９２年）の開発も行われている。In addition to the electroluminescent device using a low molecular material as described above, poly (p-phenylenevinylene) (Nature, 347, 539) is used as a material for the organic light emitting layer.
P. 1990 et al.), Poly [2-methoxy-5- (2-
Ethylhexyloxy) -1,4-phenylenevinylene] (Appl. Phys. Lett., 58, 19).
82, etc.), poly (3-alkylthiophene) (Jp
n. J. Appl. Phys., Vol. 30, L1938, etc.) and the development of an electroluminescent device using a polymer material, and a device in which a low molecular light emitting material and an electron transfer material are mixed with a polymer such as polyvinyl carbazole (Applied Physics, Vol. 61) , 10
44, 1992).
【０００５】以上に示した様な有機電界発光素子におい
ては、通常、陽極としてはインジウム錫酸化物（ＩＴ
Ｏ）のような透明電極が用いられ、陰極としては電子注
入を効率よく行うために、マグネシウム合金、アルミニ
ウム・リチウム合金、カルシウム等の仕事関数の低い金
属電極が用いられている。これらの陰極材料は大気中の
水分や酸素により容易に酸化し、その結果、陰極が有機
層から剥離し一般にダークスポット（素子の発光面にお
いて発光しない部分をさす）と呼ばれる欠陥が発生す
る。この有機電界発光素子内のダークスポットの数や大
きさは、長期間の素子の保存または駆動の際に増加し、
そのために素子の不安定性をもたらし寿命を短いものと
している。従って、有機電界発光素子の安定性を向上さ
せ信頼性を高めるためには、素子を大気中の水分や酸素
から保護するための封止が必要不可欠である。[0005] In the organic electroluminescent device as described above, indium tin oxide (IT) is usually used as an anode.
A transparent electrode such as O) is used, and a metal electrode having a low work function such as a magnesium alloy, an aluminum-lithium alloy, or calcium is used as a cathode in order to efficiently inject electrons. These cathode materials are easily oxidized by moisture or oxygen in the air, and as a result, the cathode is separated from the organic layer, and a defect generally called a dark spot (a portion which does not emit light on the light emitting surface of the device) occurs. The number and size of dark spots in the organic electroluminescent device increase when the device is stored or driven for a long time,
For this reason, instability of the element is brought about and the life is shortened. Therefore, in order to improve the stability and reliability of the organic electroluminescent device, sealing for protecting the device from moisture and oxygen in the air is indispensable.
【０００６】有機電界発光素子の封止方法として、アク
リル樹脂でモールドする方法（特開平３−３７９９１号
公報）、気密ケース内にＰ2Ｏ5とともに入れて外気から
遮断する方法（特開平３−２６１０９１号公報）、金属
の酸化物等の保護膜を設けた後にガラス板等を用いて気
密にする方法（特開平４−２１２２８４号公報）、プラ
ズマ重合膜及び光硬化型樹脂層を設ける方法（特開平５
−３６４７５号公報）、フッ素化炭素からなる不活性液
体中に保持する方法（特開平４−３６３８９０号公報
他）、高分子保護膜を設けた後シリコーンオイル中に保
持する方法（特開平５−３６４７５号公報）、無機酸化
物等の保護膜の上にポリビニルアルコールを塗布したガ
ラス板をエポキシ樹脂で接着する方法（特開平５−８９
９５９号公報）、流動パラフィンやシリコーンオイル中
に封じ込める方法（特開平５−１２９０８０号公報）、
紫外線硬化型樹脂を用いる方法（特開平５−１８２７５
９号公報他）等が開示されている。As a method of sealing an organic electroluminescent element, a method of molding with an acrylic resin (Japanese Patent Application Laid-Open No. 3-37991), a method of putting it together with P 2 O 5 in an airtight case and shielding it from the outside air (Japanese Patent Application Laid-Open No. No. 261091), a method of providing a protective film of a metal oxide or the like and then making it airtight using a glass plate or the like (Japanese Patent Laid-Open No. 4-212284), a method of providing a plasma polymerized film and a photocurable resin layer ( JP 5
JP-A-36475), a method of holding in an inert liquid made of fluorinated carbon (JP-A-4-363890, etc.), and a method of providing a polymer protective film and holding it in silicone oil (JP-A-5-305). No. 36475), a method of bonding a glass plate coated with polyvinyl alcohol on a protective film of an inorganic oxide or the like with an epoxy resin (JP-A-5-89).
959), a method of enclosing in liquid paraffin or silicone oil (JP-A-5-129080),
A method using an ultraviolet curable resin (JP-A-5-18275)
No. 9, etc.) and the like are disclosed.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、従来の
有機電界発光素子の封止方法はいずれも満足できるもの
ではなかった。例えば、吸湿剤とともに気密構造に素子
を封じ込めただけの方法はダークスポットの抑制が不十
分である。また、フッ素化炭素（例えば、商品名フロリ
ナート）やシリコーンオイル中に保持する方法は、液体
を注入する工程を含むことにより封止工程が煩雑になる
だけではなく、ダークスポットの増加も完全には防げ
ず、むしろ液体が陰極と有機層の界面に侵入して陰極の
剥離を促進する問題もある。紫外線硬化樹脂で接着封止
する方法は、接着剤に含まれる溶剤による素子のダメー
ジや紫外線によるダメージがあり、硬化時の応力歪によ
って陰極が有機層から剥離する等が起こり実用的ではな
い。エポキシ樹脂やアクリル樹脂を用いた封止方法は、
硬化による素子のダメージが大きく、封止用の接着剤と
しては不十分なのが現状である。However, none of the conventional methods for sealing an organic electroluminescent element has been satisfactory. For example, a method in which an element is simply sealed in an airtight structure together with a moisture absorbent does not sufficiently suppress dark spots. In addition, the method of holding in fluorinated carbon (for example, Fluorinert) or silicone oil not only complicates the sealing step by including the step of injecting a liquid, but also completely reduces the increase in dark spots. However, there is also a problem that the liquid does not penetrate into the interface between the cathode and the organic layer and promotes peeling of the cathode. The method of bonding and sealing with an ultraviolet curable resin is not practical because the element contained in the adhesive is damaged by a solvent contained in the adhesive or the ultraviolet light is damaged, and the stress is distorted during curing, causing the cathode to peel off from the organic layer. The sealing method using epoxy resin or acrylic resin,
At present, the element is largely damaged by curing and is insufficient as an adhesive for sealing.
【０００８】有機電界発光素子のダークスポットによる
劣化が改善されず発光特性が不安定なことは、ファクシ
ミリ、複写機、液晶ディスプレイのバックライト等の光
源としては大きな問題であり、フラットパネル・ディス
プレイ等の表示素子としても望ましくない特性である。The fact that deterioration due to dark spots of organic electroluminescent elements is not improved and light emission characteristics are unstable is a serious problem as a light source for facsimile machines, copiers, backlights of liquid crystal displays, etc., and flat panel displays and the like. This is an undesired characteristic even as a display element.
【０００９】本発明者は上記実状に鑑み、長期間に渡っ
て安定な発光特性を維持でき、ダークスポットの発生を
抑制することができる有機電界発光素子を提供すること
を目的として鋭意検討した結果、有機電界発光素子に
（イ）ＪＩＳ Ｋ ６９１１に規定される伸びが１００
％以上、（ロ）ＪＩＳ Ｋ ６３０１に規定されるショ
アーＡ硬度が２０以上、かつ（ハ）ガラス転移点が−４
０℃以下で、−４０〜＋１００℃の温度範囲でゴム状弾
性を示す樹脂を主成分とする封止層を設けることにより
上記課題を解決することができることを見い出し、本発
明を完成するに至った。In view of the above situation, the present inventors have conducted intensive studies for the purpose of providing an organic electroluminescent device capable of maintaining stable light emitting characteristics over a long period of time and suppressing the occurrence of dark spots. The organic electroluminescent device has (a) an elongation of 100 defined in JIS K 6911.
% Or more, (b) Shore A hardness specified in JIS K 6301 is 20 or more, and (c) glass transition point is -4.
It has been found that the above problem can be solved by providing a sealing layer mainly composed of a resin exhibiting rubber-like elasticity in a temperature range of −40 ° C. to + 100 ° C. at 0 ° C. or less, and completed the present invention. Was.
【００１０】[0010]
【課題を解決するための手段】すなわち、本発明の要旨
は、基板上に、陽極、有機発光層及び陰極が積層され、
該積層物の外表面に、内側から順に保護層、封止層、外
気遮断材層が形成されてなる有機電界発光素子であっ
て、前記封止層が（イ）ＪＩＳ Ｋ ６９１１に規定さ
れる伸びが１００％以上、（ロ）ＪＩＳ Ｋ ６３０１
に規定されるショアーＡ硬度が２０以上、かつ（ハ）ガ
ラス転移点が−４０℃以下で、−４０〜＋１００℃の温
度範囲でゴム状弾性を示す樹脂を主成分とすることを特
徴とする有機電界発光素子及びその製造方法、に存す
る。That is, the gist of the present invention is that an anode, an organic luminescent layer and a cathode are laminated on a substrate,
An organic electroluminescent device in which a protective layer, a sealing layer, and an outside air-blocking material layer are sequentially formed on the outer surface of the laminate from the inside, wherein the sealing layer is defined in (A) JIS K 6911. Elongation is 100% or more, (b) JIS K6301
Characterized in that the resin has a Shore A hardness of 20 or more and a glass transition point of -40 ° C or less and a rubber-like elasticity in a temperature range of -40 to + 100 ° C as a main component. An organic electroluminescent device and a method for manufacturing the same.
【００１１】以下、本発明の有機電界発光素子の製造方
法について、図面を参照しながら説明する。図１は本発
明に用いられる一般的な有機電界発光素子の構造例を模
式的に示す断面図であり、１は基板、２は陽極、３は有
機発光層、４は陰極を各々表わす。Hereinafter, a method for manufacturing an organic electroluminescent device of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing a structure example of a general organic electroluminescent device used in the present invention, wherein 1 denotes a substrate, 2 denotes an anode, 3 denotes an organic light emitting layer, and 4 denotes a cathode.
【００１２】基板１は有機電界発光素子の支持体となる
ものであり、石英やガラスの板、金属板や金属箔、プラ
スチックフィルムやシートなどが用いられる。特にガラ
ス板や、ポリエステル、ポリメタクリレート、ポリカー
ボネート、ポリスルホンなどの透明な合成樹脂の板が好
ましい。合成樹脂基板を使用する場合にはガスバリア性
に留意する必要がある。基板のガスバリヤ性が小さすぎ
ると、基板を通過した外気により有機電界発光素子が劣
化することがあるので好ましくない。このため、合成樹
脂基板の上に緻密なシリコン酸化膜等を設けてガスバリ
ア性を確保する方法も好ましい方法の一つである。The substrate 1 serves as a support for the organic electroluminescent device, and is made of a quartz or glass plate, a metal plate or a metal foil, a plastic film or a sheet, or the like. Particularly, a glass plate or a plate of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too small, the organic electroluminescent device may be deteriorated by the outside air passing through the substrate, which is not preferable. Therefore, a method of providing a dense silicon oxide film or the like on a synthetic resin substrate to secure gas barrier properties is also one of the preferable methods.
【００１３】基板１上には陽極２が設けられるが、陽極
２は有機発光層への正孔注入の役割を果たすものであ
る。この陽極は、通常、アルミニウム、金、銀、ニッケ
ル、パラジウム、白金等の金属、インジウム及び／また
はスズの酸化物などの金属酸化物、ヨウ化銅などのハロ
ゲン化金属、カーボンブラック、あるいは、ポリ（３−
メチルチオフェン）、ポリピロール、ポリアニリン等の
導電性高分子などにより構成される。陽極２の形成は通
常、スパッタリング法、真空蒸着法などにより行われる
ことが多い。また、銀などの金属微粒子、ヨウ化銅など
の微粒子、カーボンブラック、導電性の金属酸化物微粒
子、導電性高分子微粉末などの場合には、適当なバイン
ダー樹脂溶液に分散し、基板１上に塗布することにより
陽極２を形成することもできる。さらに、導電性高分子
の場合は電解重合により直接基板１上に薄膜を形成した
り、基板１上に導電性高分子を塗布して陽極２を形成す
ることもできる（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，６
０巻，２７１１頁，１９９２年）。陽極２は異なる物質
で積層して形成することも可能である。陽極２の厚み
は、必要とする透明性により異なる。透明性が必要とさ
れる場合は、可視光の透過率を、通常、６０％以上、好
ましくは８０％以上とすることが望ましく、この場合、
厚みは、通常、５〜１０００ｎｍ、好ましくは１０〜５
００ｎｍ程度である。不透明でよい場合は陽極２は基板
１と同一でもよい。また、さらには上記の陽極２の上に
異なる導電材料を積層することも可能である。An anode 2 is provided on a substrate 1. The anode 2 plays a role of injecting holes into an organic light emitting layer. This anode is usually made of a metal such as aluminum, gold, silver, nickel, palladium, and platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; carbon black; (3-
(Methylthiophene), conductive polymers such as polypyrrole and polyaniline. Usually, the formation of the anode 2 is often performed by a sputtering method, a vacuum evaporation method, or the like. In the case of fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, or conductive polymer fine powder, they are dispersed in a suitable binder resin solution and To form the anode 2. Furthermore, in the case of a conductive polymer, a thin film can be formed directly on the substrate 1 by electrolytic polymerization, or the conductive polymer can be applied on the substrate 1 to form the anode 2 (Appl. Phys. Lett. , 6
0, 2711, 1992). The anode 2 can be formed by laminating different materials. The thickness of the anode 2 depends on the required transparency. When transparency is required, the transmittance of visible light is usually at least 60%, preferably at least 80%, and in this case,
The thickness is usually 5 to 1000 nm, preferably 10 to 5 nm.
It is about 00 nm. If opaque, the anode 2 may be the same as the substrate 1. Further, it is also possible to laminate a different conductive material on the anode 2.
【００１４】陽極２の上には有機発光層３が設けられ
る。有機発光層３は、電界を与えられた電極間におい
て、陽極２から注入された正孔と陰極４から注入された
電子を効率よく輸送して再結合させ、かつ、再結合によ
り効率よく発光する材料から形成される。通常、この有
機発光層３は発光効率の向上のために、図２に示すよう
に、正孔輸送層３ａと電子輸送層３ｂに分割して機能分
離型にすることが行われる（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅ
ｔｔ．，５１巻，９１３頁，１９８７年）。An organic light emitting layer 3 is provided on the anode 2. The organic light emitting layer 3 efficiently transports the holes injected from the anode 2 and the electrons injected from the cathode 4 and recombine between the electrodes to which an electric field is applied, and emits light efficiently by the recombination. Formed from material. Normally, as shown in FIG. 2, the organic light emitting layer 3 is divided into a hole transport layer 3a and an electron transport layer 3b to be of a function-separated type in order to improve luminous efficiency (Appl. Phys. .Le
tt. 51, 913, 1987).
【００１５】上記の機能分離型素子において、正孔輸送
層３ａの材料としては、陽極２からの正孔注入効率が高
く、かつ、注入された正孔を効率よく輸送することがで
きる材料であることが必要である。そのためには、イオ
ン化ポテンシャルが小さく、しかも正孔移動度が大き
く、さらに安定性に優れ、トラップとなる不純物が製造
時や使用時に発生しにくいことが要求される。In the above function-separated element, the material of the hole transport layer 3a is a material having a high hole injection efficiency from the anode 2 and capable of efficiently transporting the injected holes. It is necessary. For that purpose, it is required that the ionization potential is small, the hole mobility is large, the stability is further excellent, and impurities serving as traps are hardly generated during production or use.
【００１６】このような正孔輸送材料としては、例え
ば、１，１−ビス（４−ジ−ｐ−トリルアミノフェニ
ル）シクロヘキサン等の３級芳香族アミンユニットを連
結した芳香族ジアミン化合物（特開昭５９−１９４３９
３号公報）、４，４’−ビス［Ｎ−（１−ナフチル）−
Ｎ−フェニルアミノ］ビフェニルで代表される２個以上
の３級アミンを含み２個以上の縮合芳香族環が窒素原子
に置換した芳香族アミン（特開平５−２３４６８１号公
報）、トリフェニルベンゼンの誘導体でスターバースト
構造を有する芳香族トリアミン（米国特許第４，９２
３，７７４号）、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビ
ス（３−メチルフェニル）ビフェニル−４，４’−ジア
ミン等の芳香族ジアミン（米国特許第４，７６４，６２
５号）、α，α，α’，α’−テトラメチル−α，α’
−ビス（４−ジ−ｐ−トリルアミノフェニル）−ｐ−キ
シレン（特開平３−２６９０８４号公報）、分子全体と
して立体的に非対称なトリフェニルアミン誘導体（特開
平４−１２９２７１号公報）、ピレニル基に芳香族ジア
ミノ基が複数個置換した化合物（特開平４−１７５３９
５号公報）、エチレン基で３級芳香族アミンユニットを
連結した芳香族ジアミン（特開平４−２６４１８９号公
報）、スチリル構造を有する芳香族ジアミン（特開平４
−２９０８５１号公報）、チオフェン基で芳香族３級ア
ミンユニットを連結したもの（特開平４−３０４４６６
号公報）、スターバースト型芳香族トリアミン（特開平
４−３０８６８８号公報）、ベンジルフェニル化合物
（特開平４−３６４１５３号公報）、フルオレン基で３
級アミンを連結したもの（特開平５−２５４７３号公
報）、トリアミン化合物（特開平５−２３９４５５号公
報）、ビスジピリジルアミノビフェニル（特開平５−３
２０６３４号公報）、Ｎ，Ｎ，Ｎ−トリフェニルアミン
誘導体（特開平６−１９７２号公報）、フェノキサジン
構造を有する芳香族ジアミン（特願平５−２９０７２８
号）、ジアミノフェニルフェナントリジン誘導体（特願
平６−４５６６９号）、ヒドラゾン化合物（特開平２−
３１１５９１号公報）、シラザン化合物（米国特許第
４，９５０，９５０号公報）、シラナミン誘導体（特開
平６−４９０７９号公報）、ホスファミン誘導体（特開
平６−２５６５９号公報）、キナクリドン化合物等が挙
げられる。これらの化合物は、単独で用いてもよいし、
必要に応じて、各々、混合して用いてもよい。As such a hole transport material, for example, an aromatic diamine compound in which tertiary aromatic amine units such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane are linked (Japanese Patent Laid-Open Publication No. 1959-19439
No. 3), 4,4'-bis [N- (1-naphthyl)-
Aromatic amines containing two or more tertiary amines represented by [N-phenylamino] biphenyl and having two or more condensed aromatic rings substituted with nitrogen atoms (JP-A-5-234681); Aromatic triamines having a starburst structure in derivatives (US Pat. No. 4,92
Aromatic diamines such as N, N'-diphenyl-N, N'-bis (3-methylphenyl) biphenyl-4,4'-diamine (U.S. Pat. No. 4,764,62)
No. 5), α, α, α ′, α′-tetramethyl-α, α ′
-Bis (4-di-p-tolylaminophenyl) -p-xylene (JP-A-3-269084), triphenylamine derivatives which are sterically asymmetric as a whole molecule (JP-A-4-129271), pyrenyl In which a plurality of aromatic diamino groups are substituted on a group (JP-A-4-17539)
No. 5), an aromatic diamine in which a tertiary aromatic amine unit is linked by an ethylene group (JP-A-4-264189), an aromatic diamine having a styryl structure (JP-A-Hei-4).
(Japanese Patent Application Laid-Open No. Hei 4-290466), a compound in which an aromatic tertiary amine unit is linked by a thiophene group
JP-A-4-308688), a benzylphenyl compound (JP-A-4-364153), and a fluorene group of 3
Tertiary amine compound (JP-A-5-239455), bisdipyridylaminobiphenyl (JP-A-5-3473)
No. 20634), N, N, N-triphenylamine derivatives (JP-A-6-1972), and aromatic diamines having a phenoxazine structure (Japanese Patent Application No. 5-290728).
), Diaminophenylphenanthridine derivatives (Japanese Patent Application No. 6-45669), hydrazone compounds (Japanese Unexamined Patent Application Publication No.
315991), silazane compounds (US Pat. No. 4,950,950), silanamin derivatives (JP-A-6-49079), phosphamine derivatives (JP-A-6-25659), quinacridone compounds and the like. . These compounds may be used alone,
If necessary, they may be mixed and used.
【００１７】上記の化合物以外に、正孔輸送層３ａの材
料として、ポリビニルカルバゾールやポリシラン（Ａｐ
ｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５９巻，２７６０頁，１
９９１年）、ポリフォスファゼン（特開平５−３１０９
４９号公報）、ポリアミド（特開平５−３１０９４９号
公報）、ポリビニルトリフェニルアミン（特願平５−２
０５３７７）、トリフェニルアミン骨格を有する高分子
（特開平４−１３３０６５号公報）、トリフェニルアミ
ン単位をメチレン基等で連結した高分子（Ｓｙｎｔｈｅ
ｔｉｃ Ｍｅｔａｌｓ，５５−５７巻，４１６３頁，１
９９３年）、芳香族アミンを含有するポリメタクリレー
ト（Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．，Ｐｏｌｙｍ．Ｃｈｅ
ｍ．Ｅｄ．，２１巻，９６９頁，１９８３年）等の高分
子材料が挙げられる。In addition to the above compounds, as a material of the hole transport layer 3a, polyvinyl carbazole or polysilane (Ap
pl. Phys. Lett. 59, 2760, 1
991), polyphosphazene (JP-A-5-3109)
No. 49), polyamide (JP-A-5-310949), polyvinyl triphenylamine (Japanese Patent Application No. 5-2).
05377), a polymer having a triphenylamine skeleton (Japanese Patent Application Laid-Open No. 4-133065), and a polymer in which triphenylamine units are linked by a methylene group or the like (Synthe).
tic Metals, 55-57, 4163, 1
993), polymethacrylates containing aromatic amines (J. Polym. Sci., Polym. Che.
m. Ed. , 21, 969, 1983).
【００１８】上記の正孔輸送材料を塗布法あるいは真空
蒸着法により前記陽極２上に積層することにより正孔輸
送層３ａを形成する。塗布法の場合は、正孔輸送材料を
１種または２種以上と、必要により正孔のトラップにな
らないバインダー樹脂や塗布性改良剤などの添加剤とを
添加し、溶解して塗布溶液を調製し、スピンコート法な
どの方法により陽極２上に塗布し、乾燥して有機正孔輸
送層３ａを形成する。バインダー樹脂としては、ポリカ
ーボネート、ポリアリレート、ポリエステル等が挙げら
れる。バインダー樹脂は添加量が多いと正孔移動度を低
下させるので、少ない方が望ましく、通常、５０重量％
以下が好ましい。The hole transport layer 3a is formed by laminating the above hole transport material on the anode 2 by a coating method or a vacuum deposition method. In the case of the coating method, one or more hole transport materials and, if necessary, an additive such as a binder resin or a coating improver which does not trap holes are added and dissolved to prepare a coating solution. Then, it is applied on the anode 2 by a method such as spin coating, and dried to form the organic hole transport layer 3a. Examples of the binder resin include polycarbonate, polyarylate, and polyester. If the amount of the binder resin is large, the hole mobility is lowered, so that a small amount is desirable, and usually 50% by weight.
The following is preferred.
【００１９】真空蒸着法の場合には、正孔輸送材料を真
空容器内に設置されたルツボに入れ、真空容器内を適当
な真空ポンプで１０-４Ｐａ程度にまで排気した後、ル
ツボを加熱して、正孔輸送材料を蒸発させ、ルツボと向
き合って置かれた基板１上の陽極２上に正孔輸送層３ａ
を形成させる。In the case of the vacuum evaporation method, the hole transporting material is put into a crucible placed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 −4 Pa by a suitable vacuum pump, and then the crucible is heated. Then, the hole transport material is evaporated, and the hole transport layer 3a is formed on the anode 2 on the substrate 1 placed facing the crucible.
Is formed.
【００２０】上記正孔輸送層３ａを形成する場合、さら
に、アクセプタとして、芳香族カルボン酸の金属錯体及
び／または金属塩（特開平４−３２０４８４号公報）、
ベンゾフェノン誘導体およびチオベンゾフェノン誘導体
（特開平５−２９５３６１号公報）、フラーレン類（特
開平５−３３１４５８号公報）等を１０-3〜１０重量％
の濃度でドープして、フリーキャリアとしての正孔を生
成させることにより、低電圧駆動を可能にすることがで
きる。In the case of forming the hole transport layer 3a, a metal complex and / or metal salt of an aromatic carboxylic acid is further used as an acceptor (Japanese Patent Laid-Open No. 4-320484).
Benzophenone derivatives and thiobenzophenone derivatives (JP-A-5-295361), fullerenes (JP-A-5-331458), etc., in an amount of 10 -3 to 10% by weight.
, To generate holes as free carriers, thereby enabling low-voltage driving.
【００２１】正孔輸送層３ａの膜厚は、通常、１０〜３
００ｎｍ、好ましくは３０〜１００ｎｍである。この様
に薄い膜を一様に形成するためには、一般に真空蒸着法
がよく用いられる。The thickness of the hole transport layer 3a is usually 10 to 3
00 nm, preferably 30 to 100 nm. In order to uniformly form such a thin film, generally, a vacuum deposition method is often used.
【００２２】正孔注入の効率をさらに向上させ、かつ、
有機層全体の陽極への付着力を改善させる目的で、正孔
輸送層３ａと陽極２との間に正孔注入層３ａ’を挿入す
ることも行われている（図３）。正孔注入層３ａ’に用
いられる材料としてはイオン化ポテンシャルが低く、導
電性が高く、さらに陽極上で熱的に安定な薄膜を形成す
る材料が望ましく、フタロシアニン化合物やポルフィリ
ン化合物（特開昭５７−５１７８１号公報、特開昭６３
−２９５６９５号公報）が使用される。正孔注入層３
ａ’を挿入することで、初期の素子の駆動電圧が下がる
と同時に、素子を定電流で連続駆動した時の電圧上昇も
抑制される効果がある。正孔注入層３ａ’に正孔輸送層
３ａと同様にしてアクセプタをドープすることで導電性
を向上させることも可能である。The efficiency of hole injection is further improved, and
In order to improve the adhesion of the entire organic layer to the anode, a hole injection layer 3a 'is inserted between the hole transport layer 3a and the anode 2 (FIG. 3). As a material used for the hole injection layer 3a ', a material having a low ionization potential, high conductivity, and a thermally stable thin film on the anode is desirable, and a phthalocyanine compound or a porphyrin compound (Japanese Unexamined Patent Publication No. No. 51781, JP-A-63
No. 2,295,695) is used. Hole injection layer 3
The insertion of a 'has the effect of reducing the initial drive voltage of the element and suppressing the voltage rise when the element is continuously driven with a constant current. It is also possible to improve the conductivity by doping the hole injection layer 3a 'with an acceptor in the same manner as the hole transport layer 3a.
【００２３】正孔注入層３ａ’の膜厚は、通常、２〜１
００ｎｍ、好ましくは５〜５０ｎｍである。この様に薄
い膜を一様に形成するためには、一般に真空蒸着法がよ
く用いられる。正孔輸送層３ａの上には電子輸送層３ｂ
が設けられる。電子輸送層３ｂは、電界を与えられた電
極間において陰極からの電子を効率よく正孔輸送層３ａ
の方向に輸送することができる化合物より形成される。The thickness of the hole injection layer 3a 'is usually 2 to 1
00 nm, preferably 5 to 50 nm. In order to uniformly form such a thin film, generally, a vacuum deposition method is often used. The electron transport layer 3b is provided on the hole transport layer 3a.
Is provided. The electron transport layer 3b efficiently transfers electrons from the cathode between the electrodes to which the electric field is applied, and the hole transport layer 3a.
Formed from compounds that can be transported in the direction of
【００２４】電子輸送層３ｂに用いられる電子輸送性化
合物としては、陰極４からの電子注入効率が高く、か
つ、注入された電子を効率よく輸送することができる化
合物であることが必要である。そのためには、電子親和
力が大きく、しかも電子移動度が大きく、さらに安定性
に優れトラップとなる不純物が製造時や使用時に発生し
にくい化合物であることが要求される。The electron transporting compound used in the electron transporting layer 3b needs to be a compound having high electron injection efficiency from the cathode 4 and capable of transporting the injected electrons efficiently. For this purpose, it is required that the compound has a high electron affinity, a high electron mobility, a high stability, and an impurity which becomes a trap and hardly occurs during production or use.
【００２５】このような条件を満たす材料としては、テ
トラフェニルブタジエンなどの芳香族化合物（特開昭５
７−５１７８１号公報）、８−ヒドロキシキノリンのア
ルミニウム錯体などの金属錯体（特開昭５９−１９４３
９３号公報）、シクロペンタジエン誘導体（特開平２−
２８９６７５号公報）、ペリノン誘導体（特開平２−２
８９６７６号公報）、オキサジアゾール誘導体（特開平
２−２１６７９１号公報）、ビススチリルベンゼン誘導
体（特開平１−２４５０８７号公報、同２−２２２４８
４号公報）、ペリレン誘導体（特開平２−１８９８９０
号公報、同３−７９１号公報）、クマリン化合物（特開
平２−１９１６９４号公報、同３−７９２号公報）、希
土類錯体（特開平１−２５６５８４）、ジスチリルピラ
ジン誘導体（特開平２−２５２７９３号公報）、ｐ−フ
ェニレン化合物（特開平３−３３１８３号公報）、チア
ジアゾロピリジン誘導体（特開平３−３７２９２号公
報）、ピロロピリジン誘導体（特開平３−３７２９３号
公報）、ナフチリジン誘導体（特開平３−２０３９８２
号公報）などが挙げられる。Materials satisfying such conditions include aromatic compounds such as tetraphenylbutadiene (Japanese Unexamined Patent Publication No.
And metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP-A-59-1943).
No. 93), cyclopentadiene derivatives (Japanese Unexamined Patent Publication No.
289675), perinone derivatives (JP-A 2-2)
No. 89676), oxadiazole derivatives (Japanese Patent Application Laid-Open No. 2-216991), and bisstyrylbenzene derivatives (Japanese Patent Application Laid-Open Nos. 1-245087 and 2-222448).
No. 4), perylene derivatives (JP-A-2-189890)
JP-A-3-7991), coumarin compounds (JP-A-2-191694 and JP-A-3-792), rare-earth complexes (JP-A-1-256584), distyrylpyrazine derivatives (JP-A-2-252793) Gazette), p-phenylene compound (JP-A-3-33183), thiadiazolopyridine derivative (JP-A-3-37292), pyrrolopyridine derivative (JP-A-3-37293), naphthyridine derivative (JP-A-3-37293). Kaihei 3-2033982
Publication).
【００２６】これらの化合物を用いた電子輸送層３ｂ
は、一般に、電子を輸送する役割と、正孔と電子の再結
合の際に発光をもたらす役割を同時に果たすことができ
る。正孔輸送層３ａが発光機能を有する場合は、電子輸
送層３ｂは電子を輸送する役割だけを果たす場合もあ
る。Electron transport layer 3b using these compounds
Can generally play a role of transporting electrons and a role of providing light emission upon recombination of holes and electrons. When the hole transport layer 3a has a light emitting function, the electron transport layer 3b may only play a role of transporting electrons.
【００２７】素子の発光効率を向上させるとともに発光
色を変える目的で、例えば、８−ヒドロキシキノリンの
アルミニウム錯体をホスト材料として、クマリン等のレ
ーザ用蛍光色素をドープすること（Ｊ．Ａｐｐｌ．Ｐｈ
ｙｓ．，６５巻，３６１０頁，１９８９年）等も行われ
ている。本発明においても上記の有機電子輸送材料をホ
スト材料として各種の蛍光色素を１０-3〜１０モル％ド
ープすることにより、素子の発光特性をさらに向上させ
ることができる。電子輸送層３ｂの膜厚は、通常、１０
〜２００ｎｍ、好ましくは３０〜１００ｎｍである。For the purpose of improving the luminous efficiency of the device and changing the luminescent color, for example, doping a fluorescent dye for laser such as coumarin with an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. Ph.
ys. 65, 3610, 1989). Also in the present invention, the light emitting characteristics of the device can be further improved by doping various fluorescent dyes with the organic electron transporting material as a host material at 10 −3 to 10 mol%. The thickness of the electron transport layer 3b is usually 10
２００200 nm, preferably 30-100 nm.
【００２８】電子輸送層も正孔輸送層と同様の方法で形
成することができるが、通常は真空蒸着法が用いられ
る。有機電界発光素子の発光効率をさらに向上させる方
法として、電子輸送層３ｂの上にさらに他の電子輸送層
３ｃを積層することもできる。この電子輸送層３ｃに用
いられる化合物には、陰極からの電子注入が容易で、電
子の輸送能力がさらに大きいことが要求される。この様
な電子輸送材料としては、オキサジアゾール誘導体（Ａ
ｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５５巻，１４８９頁，
１９８９年他）やそれらをポリメタクリル酸メチル（Ｐ
ＭＭＡ）等の樹脂に分散した系（Ａｐｐｌ．Ｐｈｙｓ．
Ｌｅｔｔ．，６１巻，２７９３頁，１９９２年）、フェ
ナントロリン誘導体（特開平５−３３１４５９号公
報）、または、ｎ型水素化非晶質炭化シリコン、ｎ型硫
化亜鉛、ｎ型セレン化亜鉛等が挙げられる。電子輸送層
３ｃの膜厚は、通常、５〜２００ｎｍ、好ましくは１０
〜１００ｎｍである。The electron transporting layer can be formed in the same manner as the hole transporting layer, but usually, a vacuum evaporation method is used. As a method for further improving the luminous efficiency of the organic electroluminescent device, another electron transport layer 3c can be further laminated on the electron transport layer 3b. The compound used for the electron transporting layer 3c is required to be capable of easily injecting electrons from the cathode and having a higher electron transporting ability. As such an electron transport material, an oxadiazole derivative (A
ppl. Phys. Lett. 55, 1489,
1989 et al.) And polymethyl methacrylate (P
MMA) or the like dispersed in a resin (Appl. Phys.
Lett. 61, p. 2793, 1992), phenanthroline derivatives (Japanese Patent Application Laid-Open No. 5-331559), n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, and the like. The thickness of the electron transporting layer 3c is usually 5 to 200 nm, preferably 10 to 200 nm.
１００100 nm.
【００２９】機能分離を行わない単層型の有機発光層３
としては、先に挙げたポリ（ｐ−フェニレンビニレン）
（Ｎａｔｕｒｅ，３４７巻，５３９頁，１９９０年
他）、ポリ［２−メトキシ−５−（２−エチルヘキシル
オキシ）−１，４−フェニレンビニレン］（Ａｐｐｌ．
Ｐｈｙｓ．Ｌｅｔｔ．，５８巻，１９８２頁，１９９１
年他）、ポリ（３−アルキルチオフェン）（Ｊｐｎ．
Ｊ．Ａｐｐｌ．Ｐｈｙｓ，３０巻，Ｌ１９３８頁，１９
９１年他）等の高分子材料や、ポリビニルカルバゾール
等の高分子に発光材料と電子移動材料を混合した系（応
用物理，６１巻，１０４４頁，１９９２年）等が挙げら
れる。Single-layer organic light emitting layer 3 without function separation
Are the poly (p-phenylenevinylene) listed above.
(Nature, 347, 539, 1990 et al.), Poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] (Appl.
Phys. Lett. 58, 1982, 1991.
Year, etc.), poly (3-alkylthiophene) (Jpn.
J. Appl. Phys, 30, L1938, 19
(1991, etc.), and a system in which a light emitting material and an electron transfer material are mixed with a polymer such as polyvinyl carbazole (Applied Physics, Vol. 61, p. 1044, 1992).
【００３０】陰極４は、有機発光層３に電子を注入する
役割を果たす。陰極４として用いられる材料は、前記陽
極２に使用される材料を用いることが可能であるが、効
率よく電子注入を行なうには、仕事関数の低い金属が好
ましく、スズ、マグネシウム、インジウム、カルシウ
ム、アルミニウム、銀等の適当な金属またはそれらの合
金が用いられる。陰極４の膜厚は通常、陽極２と同様で
ある。低仕事関数金属から成る陰極を保護する目的で、
この上にさらに、仕事関数が高く大気に対して安定な金
属層を積層することは素子の安定性を増す。この目的の
ために、アルミニウム、銀、ニッケル、クロム、金、白
金等の金属が使われる。The cathode 4 plays a role of injecting electrons into the organic light emitting layer 3. As the material used for the cathode 4, the material used for the anode 2 can be used, but for efficient electron injection, a metal having a low work function is preferable, and tin, magnesium, indium, calcium, A suitable metal such as aluminum or silver or an alloy thereof is used. The thickness of the cathode 4 is usually the same as that of the anode 2. In order to protect the cathode made of low work function metal,
Furthermore, laminating a metal layer having a high work function and being stable to the atmosphere increases the stability of the device. For this purpose, metals such as aluminum, silver, nickel, chromium, gold, platinum and the like are used.
【００３１】第１〜３図に示した構造以外にも、以下に
示すような層構成の有機電界発光素子が本発明に用いら
れる；In addition to the structure shown in FIGS. 1 to 3, an organic electroluminescent device having the following layer structure is used in the present invention;
【００３２】[0032]
【表１】 [Table 1]
【００３３】上記層構成で、界面層は陰極と有機層との
コンタクトを向上させるためのもので、芳香族ジアミン
化合物（特開平６−２６７６５８号公報）、キナクリド
ン化合物（特願平５−１１６２０４号）、ナフタセン誘
導体（特願平５−１１６２０５号）、有機シリコン化合
物（特願平５−１１６２０６号）、有機リン化合物（特
願平５−１１６２０７号）、Ｎ−フェニルカルバゾール
骨格を有する化合物（特願平６−１９９５６２号）、Ｎ
−ビニルカルバゾール重合体（特願平６−２００９４２
号）等で構成された層が例示できる。界面層の膜厚は、
通常、２〜１００ｎｍ、好ましくは５〜３０ｎｍであ
る。界面層を設ける代わりに、有機発光層及び電子輸送
層の陰極界面近傍に上記界面層の材料を５０重量％以上
含む領域を設けてもよい。In the above layer structure, the interface layer is for improving the contact between the cathode and the organic layer, and includes an aromatic diamine compound (Japanese Patent Application Laid-Open No. 6-267658) and a quinacridone compound (Japanese Patent Application No. 5-116204). ), A naphthacene derivative (Japanese Patent Application No. 5-116205), an organic silicon compound (Japanese Patent Application No. 5-116206), an organic phosphorus compound (Japanese Patent Application No. 5-116207), and a compound having an N-phenylcarbazole skeleton (Japanese Patent Application No. 5-116207). No. 6-199562), N
-Vinylcarbazole polymer (Japanese Patent Application No. 6-200942)
No.) and the like. The thickness of the interface layer is
Usually, it is 2 to 100 nm, preferably 5 to 30 nm. Instead of providing the interface layer, a region containing 50% by weight or more of the material for the interface layer may be provided near the cathode interface between the organic light emitting layer and the electron transport layer.
【００３４】有機電界発光素子の安定性及び信頼性を向
上させるために素子全体を封止する必要がある。以下
に、本発明の封止方法を図４の構造例を用いて説明す
る。ダークスポットを抑制するためには、先ず、素子を
気密な構造中に置かなければならない。その際に、密閉
された空間内に自由体積があると、ダークスポットの抑
制が困難なことが判明した。この理由としては、陰極４
の有機発光層３に対する付着力が非常に弱いために、陰
極４の近傍に自由体積が存在すると駆動時の発熱等によ
り容易に陰極４が有機発光層３から剥離するためと考え
られる。この点において、不活性気体や不活性液体で封
止する方法ではダークスポットの回避は困難である。従
って、何等かの固体状態の材料で密閉された空間を埋め
尽くす必要があるが、従来のアクリル樹脂、エポキシ樹
脂、シアノアクリレート樹脂、紫外線硬化型樹脂等の接
着剤を用いたのでは、封止層が硬いために硬化時に発生
する硬化収縮歪や内部応力が有機電界発光素子との接着
部界面に集中するために、陰極４の剥離が激しくなった
り、素子が短絡したりする。In order to improve the stability and reliability of the organic electroluminescent device, it is necessary to seal the entire device. Hereinafter, the sealing method of the present invention will be described with reference to the structural example of FIG. To suppress dark spots, the device must first be placed in an airtight structure. At that time, it was found that it was difficult to suppress dark spots if there was a free volume in the closed space. The reason for this is that the cathode 4
It is considered that because the adhesive force of the organic light emitting layer 3 to the organic light emitting layer 3 is very weak, if a free volume exists in the vicinity of the cathode 4, the cathode 4 is easily separated from the organic light emitting layer 3 due to heat generation during driving or the like. In this regard, it is difficult to avoid dark spots by the method of sealing with an inert gas or an inert liquid. Therefore, it is necessary to fill the closed space with some solid-state material, but if an adhesive such as a conventional acrylic resin, epoxy resin, cyanoacrylate resin, and ultraviolet curing resin is used, the Since the layer is hard, the curing shrinkage strain and internal stress generated during curing concentrate on the interface of the bonding portion with the organic electroluminescent element, so that the cathode 4 is severely peeled or the element is short-circuited.
【００３５】封止層６の材料として従来の封止剤とは異
なる、下記（イ）、（ロ）、（ハ）の条件を満足する樹
脂が有機電界発光素子の封止剤として最適なことを本発
明者は見い出した。 （イ）ＪＩＳ Ｋ ６９１１に規定される伸びが１００
％以上。 （ロ）ＪＩＳ Ｋ ６３０１に規定されるショアーＡ硬
度が２０以上。 （ハ）ガラス転移点が−４０℃以下で、−４０〜＋１０
０℃の温度範囲でゴム状弾性を示す。As a material for the sealing layer 6, a resin satisfying the following conditions (A), (B) and (C), which is different from the conventional sealing agent, is most suitable as the sealing agent for the organic electroluminescent device. The present inventor has found. (B) The elongation specified in JIS K 6911 is 100
%that's all. (B) Shore A hardness specified in JIS K6301 is 20 or more. (C) a glass transition point of −40 ° C. or lower and −40 to +10
It exhibits rubbery elasticity in the temperature range of 0 ° C.
【００３６】前記のゴム状弾性とは、通常、著しく小さ
い弾性率と数百％にも及ぶヒズミの可逆弾性域を持つ状
態をいい、例えば、剪断弾性率が１０7〜１０9ｄｙｎｅ
／ｃｍ2（１０6〜１０8Ｎ／ｍ2）程度となる状態をい
う。前記の特性を満たす封止剤として、変性シリコーン
系弾性接着剤が例示できる。変性シリコーン系弾性接着
剤は反応性シリル基末端を有し、該シリル基が水分等と
反応して架橋する、通称、特殊シリコーン変性ポリマー
と称される樹脂をベースとする接着剤であり、代表的な
変性シリコーン系弾性接着剤としては、反応性シリル基
末端を有するベース樹脂を主とする成分と、シリル基と
反応して結合する官能基を有する化合物を主とする成分
との２成分からなる接着剤が例示できる。前記のシリル
基と反応して結合する官能基を有する化合物の好ましい
例として、ビスフェノールＡジグリシジルエーテル等の
エポキシ樹脂が挙げられる。The above-mentioned rubbery elasticity usually means a state having a remarkably small elastic modulus and a reversible elastic range of several hundred percent of a strain. For example, the shear elastic modulus is 10 7 to 10 9 dyne.
/ Cm 2 (10 6 to 10 8 N / m 2 ). Examples of the sealant satisfying the above-mentioned properties include a modified silicone elastic adhesive. Modified silicone-based elastic adhesives are resins based adhesives having a reactive silyl group end, and the silyl group reacts with moisture or the like to crosslink, and is generally called a special silicone-modified polymer. As a typical modified silicone elastic adhesive, there are two components: a component mainly comprising a base resin having a reactive silyl group terminal; and a component mainly comprising a compound having a functional group which reacts with and binds to a silyl group. Can be exemplified. Preferred examples of the compound having a functional group that reacts with and binds to the silyl group include an epoxy resin such as bisphenol A diglycidyl ether.
【００３７】反応性シリル基末端を有するベース樹脂と
してはポリプロピレンオキシドの末端をシリル変性した
樹脂、例えば以下の構造式に示す化合物、As the base resin having a reactive silyl group terminal, a resin obtained by silyl-modifying the terminal of polypropylene oxide, for example, a compound represented by the following structural formula:
【００３８】[0038]
【化１】 Embedded image
【００３９】が例示できる。このポリマーは、水分との
加水分解反応により分子鎖延長反応と架橋反応が進行し
てゴム状弾性体となる。上記に示した変性シリコーン系
弾性接着剤のガラス転移温度は約−６０℃であり、硬化
後の特性としては−６０℃から１２０℃までの温度範囲
でゴム状弾性を示し、従来のエポキシ樹脂と比べて約３
ケタ小さい剛性率を示し、ショアー硬度は４０〜９０の
範囲である。この結果、この変性シリコーン系弾性接着
剤の特徴としては、硬化時に発生する硬化収縮歪や外部
からの機械的応力と被着剤との線膨張係数の差等から発
生する内部応力歪を接着層で吸収分散させ、接着部界面
の残留応力が小さく、適度な接着力で陰極４を有機発光
層３に押し付け、陰極４の剥離を防ぐ効果が挙げられ
る。さらに、サーマルショックやヒートサイクルにも強
く信頼性の高い接着剤である。Can be exemplified. This polymer undergoes a hydrolysis reaction with water to undergo a molecular chain extension reaction and a crosslinking reaction, and becomes a rubber-like elastic body. The glass transition temperature of the modified silicone-based elastic adhesive shown above is about -60 ° C, and the properties after curing show rubber-like elasticity in a temperature range from -60 ° C to 120 ° C. About 3
It shows an order of magnitude less rigidity and Shore hardness in the range of 40-90. As a result, the characteristics of this modified silicone-based elastic adhesive are as follows: curing shrinkage strain generated at the time of curing, and internal stress strain generated due to a difference in a linear expansion coefficient between an external mechanical stress and an adherend, and the like. And the residual stress at the interface of the bonding portion is small, and the cathode 4 is pressed against the organic light emitting layer 3 with an appropriate bonding force to prevent the cathode 4 from peeling. Furthermore, it is a highly reliable adhesive that is resistant to thermal shock and heat cycles.
【００４０】具体的な変性シリコーン系弾性接着剤とし
ては、セメダイン社のＰＭ１６５、ＰＭ２００、ＰＭ４
００、ＥＰ００１、コニシ社のＭＯＳ７等の商品名で市
販されている弾性接着剤が挙げられる。また硬化速度を
さらに大きくするためにシアノアクリレートをさらに配
合したセメダイン社のペグα（商品名）等も封止用接着
剤として効果的である。これらは通常、常温硬化型であ
る。Specific examples of modified silicone-based elastic adhesives include Cemedine's PM165, PM200, and PM4.
Elastic adhesives commercially available under trade names such as 00, EP001 and Konishi's MOS7. In addition, Peg α (trade name) of Cemedine, which further contains cyanoacrylate in order to further increase the curing rate, is also effective as a sealing adhesive. These are usually cold-setting.
【００４１】封止層としての効果をさらに高めるため
に、フィラーとしてシリカゲル、ゼオライト、塩化カル
シウム、活性炭、ナイロン及びポリビニルアルコール等
の吸湿剤を上記の変性シリコーーン系弾性接着剤に含有
させることもさらに効果的である。フィラーの含有量と
しては、通常、１０〜５０重量％の範囲が好ましい。In order to further enhance the effect as a sealing layer, it is also effective to include a moisture absorbent such as silica gel, zeolite, calcium chloride, activated carbon, nylon and polyvinyl alcohol as a filler in the modified silicone adhesive. It is a target. Usually, the content of the filler is preferably in the range of 10 to 50% by weight.
【００４２】前記封止層６を設ける際に、陰極４にかか
る応力を緩和し、さらに、封止層に用いられる接着剤の
化学成分と素子の反応を抑制して素子に対するダメージ
を防ぐ目的で、陰極４と封止層６の間に保護層５を設け
ることが必要である。保護層５の材料としては、電気絶
縁性を有しかつ膜形状が安定で素子にダメージを与えな
い材料であれば無機材料でも有機材料でもよい。保護層
５の材料の具体例としては、金属の酸化物（特開平４−
２１２２８４号公報、特開平４−７３８８６号公報、特
開平５−３３５０８０号公報）、金属のフッ化物（特開
平４−２１２２８４号公報）、金属の硫化物（特開平４
−２１２２８４号公報）、金属の窒化物（特開平４−７
３８８６号公報）、高分子（特開平４−１３７４８３号
公報、特開平４−２０６３８６号公報、特開平４−２３
３１９２号公報、特開平４−２６７０９７号公報、特開
平４−３５５０９６号公報）、プラズマ重合膜（特開平
５−１０１８８６号公報）、有機シリコン化合物、有機
電界発光素子の有機組成物等が挙げられるが、これらに
限定されるものではない。保護層５の膜厚は、通常、５
０ｎｍ〜１０μｍ、好ましくは、１００ｎｍ〜１μｍで
ある。When the sealing layer 6 is provided, the stress applied to the cathode 4 is alleviated, and furthermore, the chemical components of the adhesive used for the sealing layer and the reaction of the element are suppressed to prevent damage to the element. It is necessary to provide a protective layer 5 between the cathode 4 and the sealing layer 6. As a material of the protective layer 5, an inorganic material or an organic material may be used as long as the material has electrical insulation properties, a stable film shape and does not damage the element. As a specific example of the material of the protective layer 5, a metal oxide (Japanese Unexamined Patent Publication No.
JP-A-212284, JP-A-4-73886, JP-A-5-335080), metal fluorides (JP-A-4-212284), and metal sulfides (JP-A-4-212284).
JP-A-212284), metal nitrides (Japanese Unexamined Patent Publication No.
No. 3886), polymers (JP-A-4-137483, JP-A-4-206386, JP-A-4-23)
No. 3,192, JP-A-4-267097, JP-A-4-355096), a plasma-polymerized film (JP-A-5-101886), an organic silicon compound, an organic composition of an organic electroluminescent element, and the like. However, the present invention is not limited to these. The thickness of the protective layer 5 is usually 5
It is 0 nm to 10 μm, preferably 100 nm to 1 μm.
【００４３】有機電界発光素子の上に保護層５を設け、
その後封止層６を設けた後、素子を外気から遮断する外
気遮断材層７を適当な接着剤８を用いて基板１に貼り合
わせる。外気遮断材層には基板と同様にガスバリア性の
あることが要求される。このため通常は電気絶縁性ガラ
ス板や、緻密なシリコン酸化膜等が設けられた電気絶縁
性の樹脂板やフィルムが使用される。接着剤８としては
ガスバリア性を有するものであればよく、例えば、エポ
キシ系接着剤、アクリル系接着剤、ポリウレタン系接着
剤、変性シリコーン系弾性接着剤等が挙げられる。A protective layer 5 is provided on the organic electroluminescent element,
Thereafter, after providing the sealing layer 6, an outside air blocking material layer 7 for blocking the element from the outside air is bonded to the substrate 1 using an appropriate adhesive 8. The outside air blocking material layer is required to have a gas barrier property like the substrate. For this reason, an electrically insulating glass plate or an electrically insulating resin plate or film provided with a dense silicon oxide film or the like is usually used. The adhesive 8 may have a gas barrier property, and examples thereof include an epoxy adhesive, an acrylic adhesive, a polyurethane adhesive, and a modified silicone elastic adhesive.
【００４４】上記の封止方法を実際の素子作製に適用す
る際には、素子が短絡する場合が有り得る。これは、例
えば、有機発光層における空隙欠陥や作製時のゴミによ
る欠陥等が存在すると、その欠陥近傍にある陰極が封止
層からの力で空隙空間内に陥没し、結果として陰極と陽
極が短絡することによる。しかしながら、陰極４の膜厚
が有機発光層３の膜厚より小さい場合は、陰極は陥没時
に断線を起こし短絡とはならない。従って、陰極４の膜
厚が有機発光層３の膜厚より薄いことが好ましい。この
短絡現象は陽極２の表面粗さにも関係しており、陽極２
に山谷状のうねりがあると、例えば、陽極２の山の斜面
上では、有機発光層３は基板１に対して垂直に堆積され
るが、陽極２の山の斜面に対して垂直な方向で見ると、
実質上斜面の傾き分だけ有機層の膜厚は減少することに
なる。このことから、陽極２の表面粗さは基板１の表面
粗さ程度に抑えられていることが望ましく、１０点平均
粗さＲｚ（ＪＩＳで定義される）が１０ｎｍ以下である
ことが好ましい。When the above sealing method is applied to actual device fabrication, the device may be short-circuited. This is because, for example, if there is a void defect in the organic light emitting layer or a defect due to dust at the time of fabrication, the cathode in the vicinity of the defect sinks into the void space due to the force from the sealing layer, and as a result, the cathode and the anode become By short circuit. However, when the film thickness of the cathode 4 is smaller than the film thickness of the organic light emitting layer 3, the cathode is disconnected at the time of depression and does not cause a short circuit. Therefore, the thickness of the cathode 4 is preferably smaller than the thickness of the organic light emitting layer 3. This short-circuit phenomenon is also related to the surface roughness of the anode 2,
For example, if there is a valley-like undulation on the slope of the anode 2, the organic light emitting layer 3 is deposited perpendicular to the substrate 1, but in a direction perpendicular to the slope of the anode 2. Looking at it,
The thickness of the organic layer is reduced substantially by the slope of the slope. For this reason, the surface roughness of the anode 2 is desirably suppressed to about the surface roughness of the substrate 1, and the ten-point average roughness Rz (defined by JIS) is preferably 10 nm or less.
【００４５】本発明は、有機電界発光素子が、単一の素
子、アレイ状に配置された構造からなる素子、陽極と陰
極がＸ−Ｙマトリックス状に配置された構造のいずれに
おいても適用することができる。The present invention can be applied to any of a single organic electroluminescent device, a device having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. Can be.
【００４６】[0046]
【実施例】次に、本発明を実施例によって更に具体的に
説明するが、本発明はその要旨を越えない限り、以下の
実施例の記載に限定されるものではない。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the description of the following examples unless it exceeds the gist.
【００４７】実施例１ 図２に示す構造を有する有機電界発光素子を以下の方法
で作製した。ガラス基板上にインジウム・スズ酸化物
（ＩＴＯ）透明導電膜を１２０ｎｍ堆積したもの（ジオ
マテック社製；電子ビーム成膜品；シート抵抗１５Ω）
により、触針式表面粗さ計（ランクテーラーホブソン社
製タリステップ）によりＩＴＯ表面の十点平均粗さＲｚ
（ＪＩＳ Ｂ０６０１）を測定したところ７．４ｎｍで
あった。このＩＴＯガラス基板を通常のフォトリソグラ
フィ技術と塩酸エッチングを用いて２ｍｍ幅のストライ
プにパターニングして陽極を形成した。パターン形成し
たＩＴＯ基板を、アセトンによる超音波洗浄、純水によ
る水洗、イソプロピルアルコールによる超音波洗浄の順
で洗浄後、窒素ブローで乾燥させ、最後に紫外線オゾン
洗浄を行って、真空蒸着装置内に設置した。装置の粗排
気を油回転ポンプにより行った後、装置内の真空度が２
×１０-6Ｔｏｒｒ（約２．７×１０ -4Ｐａ）以下になる
まで液体窒素トラップを備えた油拡散ポンプを用いて排
気した。上記装置内に配置されたセラミックるつぼに入
れた、以下に示す、４，４’−ビス［Ｎ−（１−ナフチ
ル）−Ｎ−フェニルアミノ］ビフェニル（Ｈ１）Example 1 An organic electroluminescent device having the structure shown in FIG.
Prepared. Indium tin oxide on glass substrate
(ITO) 120 nm of transparent conductive film deposited (Geo
(Material: Electron beam film; Sheet resistance 15Ω)
By using a stylus type surface roughness meter (Rank Taylor Hobson
10 points average roughness Rz of ITO surface
(JIS B0601) was measured and found to be 7.4 nm.
there were. This ITO glass substrate is used for ordinary photolithography.
2mm-wide stripe using phi technology and hydrochloric acid etching
An anode was formed by patterning the anode. Pattern forming
The cleaned ITO substrate is cleaned by ultrasonic cleaning with acetone and pure water.
Washing with water and ultrasonic cleaning with isopropyl alcohol
, Dry with nitrogen blow, and finally UV ozone
After cleaning, it was set in a vacuum evaporation apparatus. Rough discharge of equipment
After the air was pumped by an oil rotary pump, the degree of vacuum
× 10-6Torr (about 2.7 × 10 -FourPa)
Using an oil diffusion pump equipped with a liquid nitrogen trap.
I noticed. Enter the ceramic crucible placed in the above equipment
4,4'-bis [N- (1-naphthy)
Ru) -N-phenylamino] biphenyl (H1)
【００４８】[0048]
【化２】 Embedded image
【００４９】をるつぼの周囲のタンタル線ヒーターで加
熱して蒸着を行った。この時のるつぼの温度は、２５０
〜２６０℃の範囲で制御した。蒸着時の真空度１．７×
１０-6Ｔｏｒｒ（約２．３×１０-4Ｐａ）、蒸着時間３
分３０秒で膜厚６０ｎｍの正孔輸送層３ａを得た。The vapor was deposited by heating with a tantalum wire heater around the crucible. The temperature of the crucible at this time is 250
The temperature was controlled in the range of ２６０260 ° C. Degree of vacuum at the time of vapor deposition 1.7 ×
10 -6 Torr (about 2.3 × 10 -4 Pa), deposition time 3
A hole transport layer 3a having a thickness of 60 nm was obtained in 30 minutes.
【００５０】次に、発光機能を有する電子輸送層３ｂの
材料として、以下の構造式に示すアルミニウムの８−ヒ
ドロキシキノリン錯体、Ａl（Ｃ9Ｈ6ＮＯ）3（Ｅ１）、Next, as a material of the electron transporting layer 3b having a light emitting function, aluminum 8-hydroxyquinoline complex represented by the following structural formula, Al (C 9 H 6 NO) 3 (E1),
【００５１】[0051]
【化３】 Embedded image
【００５２】を上記正孔輸送層３ａの上に同様にして蒸
着を行った。この時のるつぼの温度は２７０〜３００℃
の範囲で制御した。蒸着時の真空度は１．３×１０-6Ｔ
ｏｒｒ（約１．７×１０-4Ｐａ）、蒸着時間は３分１０
秒で、蒸着された電子輸送層３ｂの膜厚は７５ｎｍであ
った。上記の正孔輸送層３ａ及び電子輸送層３ｂを真空
蒸着する時の基板温度は室温に保持した。Was deposited on the hole transport layer 3a in the same manner. The temperature of the crucible at this time is 270-300 ° C
Was controlled within the range. The degree of vacuum during vapor deposition is 1.3 × 10 -6 T
orr (approximately 1.7 × 10 −4 Pa), deposition time is 3 minutes 10
In seconds, the thickness of the deposited electron transport layer 3b was 75 nm. The substrate temperature during vacuum deposition of the hole transport layer 3a and the electron transport layer 3b was kept at room temperature.
【００５３】ここで、電子輸送層３ｂまでの蒸着を行っ
た素子を一度前記真空蒸着装置内より大気中に取り出し
て、陰極蒸着用のマスクとして２ｍｍ幅のストライプ状
シャドーマスクを、陽極２のＩＴＯストライプとは直交
するように素子に密着させて、別の真空蒸着装置内に設
置して有機層と同様にして装置内の真空度が２×１０ -6
Ｔｏｒｒ（約２．７×１０-4Ｐａ）以下になるまで排気
した。続いて、陰極４として、マグネシウムと銀の合金
電極を２元同時蒸着法によって膜厚１４０ｎｍとなるよ
うに蒸着した。蒸着はモリブデンボートを用いて、真空
度１×１０-5Ｔｏｒｒ（約１．３×１０-3Ｐａ）、蒸着
時間３分２０秒で行った。また、マグネシウムと銀の原
子比は１０：１．２とした。さらに続いて、装置の真空
を破らないで、アルミニウムをモリブデンボートを用い
て１１０ｎｍの膜厚でマグネシウム・銀合金膜の上に積
層して陰極４を完成させた。アルミニウム蒸着時の真空
度は１．５×１０-5Ｔｏｒｒ（約２．０×１０-3Ｐ
ａ）、蒸着時間は１分２０秒であった。以上のマグネシ
ウム・銀合金とアルミニウムの２層型陰極の蒸着時の基
板温度は室温に保持した。Here, vapor deposition up to the electron transport layer 3b is performed.
Once removed element from the vacuum evaporation system to the atmosphere
2 mm wide stripes as a mask for cathode deposition
Make the shadow mask orthogonal to the ITO stripe of anode 2.
In a vacuum deposition apparatus
And the degree of vacuum in the apparatus is 2 × 10 -6
Torr (about 2.7 × 10-FourExhaust until below Pa)
did. Then, as the cathode 4, an alloy of magnesium and silver
The electrode will be 140 nm in thickness by the binary simultaneous evaporation method.
Deposited. Vacuum deposition using a molybdenum boat
Degree 1 × 10-FiveTorr (about 1.3 × 10-3Pa), evaporation
The test was performed for 3 minutes and 20 seconds. Also, the source of magnesium and silver
The child ratio was 10: 1.2. Further, the vacuum of the device
Do not break the aluminum with a molybdenum boat
Over the magnesium-silver alloy film with a thickness of 110 nm
To complete the cathode 4. Vacuum for aluminum deposition
The degree is 1.5 × 10-FiveTorr (about 2.0 × 10-3P
a), the deposition time was 1 minute and 20 seconds. Magnesi over
Base for deposition of a two-layer cathode made of aluminum-silver alloy and aluminum
The plate temperature was kept at room temperature.
【００５４】以上の様にして、２ｍｍ×２ｍｍのサイズ
の有機電界発光素子が得られた。この素子を陰極蒸着装
置から取り出した後、次に素子の封止を行った。先ず、
既述の有機層蒸着装置に再び上記素子を設置した後、こ
れまでに示したのと同様にして、化合物（Ｈ１）を膜厚
１５０ｎｍで陰極４の上に積層して、保護層５とした。
この時の真空度は１．５×１０-6Ｔｏｒｒ（約２．０×
１０-4Ｐａ）、蒸着時間は７分３０秒、基板温度は室温
であった。素子を上記装置より大気中に取り出して、窒
素グローブボックス中に入れて以下の作業を行った。As described above, an organic electroluminescent device having a size of 2 mm × 2 mm was obtained. After removing the device from the cathode vapor deposition device, the device was sealed. First,
After installing the above element again in the organic layer vapor deposition apparatus described above, the compound (H1) was laminated on the cathode 4 in a thickness of 150 nm to form the protective layer 5 in the same manner as described above. .
The degree of vacuum at this time is 1.5 × 10 −6 Torr (about 2.0 ×
10 −4 Pa), the deposition time was 7 minutes and 30 seconds, and the substrate temperature was room temperature. The device was taken out of the above device into the atmosphere, placed in a nitrogen glove box, and the following operation was performed.
【００５５】二液混合型の変性シリコーン系弾性接着剤
（セメダイン社製、商品名ＥＰ００１）を適当量混合し
た後、重量比で約３０％のシリカゲル粉末（粒径５０〜
３００μｍ）をフィラーとしてさらに加えた後、保護層
５の上に厚さ約１ｍｍで塗布して封止層６とした。な
お、該弾性接着剤により得られた樹脂はＪＩＳ Ｋ ６
９１１に規定される伸びが２００％であり、ＪＩＳ Ｋ
６３０１に規定されるショアーＡ硬度が７８であり、
ガラス転移点が−６０℃であり、−４０〜＋１００℃の
温度領域でゴム状弾性を示した。室温で４０分硬化させ
た後、外気遮断材層７として厚さ１．１ｍｍのガラス板
を、接着部分８にエポキシ樹脂（チバガイギー社製、商
品名アラルダイト）を用いて貼り合わせ、素子の封止を
完了させた。After mixing an appropriate amount of a two-part mixed type modified silicone elastic adhesive (trade name: EP001, manufactured by Cemedine Co., Ltd.), a silica gel powder having a weight ratio of about 30% (particle size: 50 to 50%) was added.
(300 μm) was further added as a filler, and then applied on the protective layer 5 to a thickness of about 1 mm to form a sealing layer 6. The resin obtained from the elastic adhesive is JIS K6
The elongation specified in 911 is 200% and JIS K
Shore A hardness specified in 6301 is 78,
The glass transition point was −60 ° C., and showed rubber-like elasticity in a temperature range of −40 to + 100 ° C. After curing at room temperature for 40 minutes, a 1.1 mm-thick glass plate is bonded to the bonding portion 8 using an epoxy resin (trade name: Araldite, manufactured by Ciba-Geigy) as the outside air-blocking material layer 7 to seal the element. Was completed.
【００５６】この様にして得られた有機電界発光素子を
大気中で室温保存して、陽極２にプラス、陰極４にマイ
ナスの直流電圧を印加して発光させ、発光特性とダーク
スポットの発生の経時変化を測定した。ダークスポット
の測定は、素子の発光面をＣＣＤカメラにより撮影した
後、画像解析により２値化して定量化を行った。The organic electroluminescent device thus obtained was stored in the air at room temperature, and a positive DC voltage was applied to the anode 2 and a negative DC voltage was applied to the cathode 4 to emit light. The change over time was measured. For the measurement of the dark spot, the light emitting surface of the element was photographed with a CCD camera, and then binarized by image analysis to quantify.
【００５７】１１Ｖを素子に印加した時の発光輝度の経
時変化を図５に、ダークスポットの経時変化を図６に示
す。６０日間の大気保存後でも発光輝度は初期輝度の１
４７ｃｄ／ｍ2 に対して１４０ｃｄ／ｍ2 とほとんど低
下がみられず、ダークスポットは６０日後でも全発光面
積の１％未満であった。FIG. 5 shows the change over time of the light emission luminance when 11 V is applied to the element, and FIG. 6 shows the change over time of the dark spot. Even after 60 days of atmospheric storage, the emission luminance is 1 of the initial luminance.
There was almost no decrease from 140 cd / m 2 to 47 cd / m 2, and the dark spot was less than 1% of the total light emitting area even after 60 days.
【００５８】比較例１ 封止層６の材料としてエポキシ樹脂（チバガイギー社
製、商品名アラルダイト）を用いた他は実施例１と同様
にして封止素子を作製した。なお、該エポキシ樹脂はゴ
ム状弾性を示さなかった。この素子に直流８Ｖを印加し
た時の発光輝度の経時変化を図５に、ダークスポットの
経時変化を図６に示す。６０日間の大気保存後では発光
輝度は初期輝度の２８２ｃｄ／ｍ2 に対して１０３ｃｄ
／ｍ2 と４０％以下に低下し、ダークスポットは６０日
後では全発光面積の４６％にも達した。Comparative Example 1 A sealing element was manufactured in the same manner as in Example 1 except that an epoxy resin (trade name: Araldite, manufactured by Ciba-Geigy) was used as the material of the sealing layer 6. The epoxy resin did not show rubber-like elasticity. FIG. 5 shows the change over time of the light emission luminance when a direct current of 8 V is applied to this element, and FIG. 6 shows the change over time of the dark spot. After 60 days of atmospheric storage, the emission luminance is 103 cd against the initial luminance of 282 cd / m 2 .
/ M 2, which is less than 40%, and the dark spot reached 46% of the total light emitting area after 60 days.
【００５９】実施例２ 図３に示す構造を有する有機電界発光素子を以下の方法
で作製した。実施例１と同様にしてパターニング加工し
たＩＴＯガラス基板を真空蒸着装置内に設置した。装置
の粗排気を油回転ポンプにより行った後、装置内の真空
度が２×１０-6Ｔｏｒｒ（約２．７×１０-4Ｐａ）以下
になるまで液体窒素トラップを備えた油拡散ポンプを用
いて排気した。上記装置内に配置されたモリブデンボー
トに入れた以下に示す銅フタロシアニン（Ｈ２）（結晶
形はβ型）Example 2 An organic electroluminescent device having the structure shown in FIG. 3 was manufactured by the following method. An ITO glass substrate patterned in the same manner as in Example 1 was set in a vacuum evaporation apparatus. After rough exhaust of the apparatus is performed by an oil rotary pump, an oil diffusion pump equipped with a liquid nitrogen trap is used until the degree of vacuum in the apparatus becomes 2 × 10 −6 Torr (about 2.7 × 10 −4 Pa) or less. And evacuated. Copper phthalocyanine (H2) shown below in a molybdenum boat placed in the above apparatus (crystal form is β-type)
【００６０】[0060]
【化４】 Embedded image
【００６１】を加熱して蒸着を行った。真空度２×１０
-6Ｔｏｒｒ（約２．７×１０-4Ｐａ）、蒸着時間５５秒
で蒸着を行ない、膜厚２０ｎｍの正孔注入層３ａ’を得
た。次に、正孔輸送層３ａとしてセラミックるつぼに入
れた化合物（Ｈ１）を実施例１と同様にして上記の正孔
注入層３ａ’の上に積層した。真空度１．５×１０ -6Ｔ
ｏｒｒ（約２．０×１０-4Ｐａ）、蒸着時間３分３０秒
で蒸着を行ない、膜厚６０ｎｍの正孔輸送層３ａを得
た。Was heated to perform vapor deposition. Vacuum 2 × 10
-6Torr (about 2.7 × 10-FourPa), evaporation time 55 seconds
To obtain a hole injection layer 3a 'having a thickness of 20 nm.
Was. Next, it is put into a ceramic crucible as a hole transport layer 3a.
The compound (H1) thus obtained was treated with the above-mentioned hole
It was laminated on the injection layer 3a '. Vacuum 1.5 × 10 -6T
orr (about 2.0 × 10-FourPa), deposition time 3 minutes 30 seconds
To obtain a hole transport layer 3a having a thickness of 60 nm.
Was.
【００６２】引続いて、発光機能を有する電子輸送層３
ｂを化合物（Ｅ１）を用いて、実施例１と同様にして正
孔輸送層３ａの上に積層した。真空度１．５×１０-6Ｔ
ｏｒｒ（約２．０×１０-4Ｐａ）、蒸着時間２分１０秒
で蒸着を行ない、膜厚は７５ｎｍの電子輸送層３ｂを得
た。Subsequently, the electron transport layer 3 having a light emitting function
b was laminated on the hole transport layer 3a in the same manner as in Example 1 using the compound (E1). Vacuum 1.5 × 10 -6 T
Vapor deposition was performed at orr (about 2.0 × 10 −4 Pa) for a vapor deposition time of 2 minutes and 10 seconds to obtain an electron transport layer 3b having a thickness of 75 nm.
【００６３】上記の正孔注入層３ａ’、正孔輸送層３ａ
及び電子輸送層３ｂを真空蒸着する時の基板温度は室温
に保持した。ここで、電子輸送層３ｂまでの蒸着を行っ
た素子を一度前記真空蒸着装置内より大気中に取り出し
て、陰極蒸着用のマスクとして２ｍｍ幅のストライプ状
シャドーマスクを、陽極のＩＴＯストライプとは直交す
るように素子に密着させて、別の真空蒸着装置内に設置
して陰極４を以下の様に形成した。先ず、マグネシウム
と銀の合金電極を２元同時蒸着法によって膜厚５５ｎｍ
となるように蒸着した。蒸着はモリブデンボートを用
い、真空度１×１０-5Ｔｏｒｒ（約１．３×１０ -3Ｐ
ａ）、蒸着時間１分１５秒で、マグネシウムと銀の原子
比を１０：１として行なった。さらに続いて、装置の真
空を破らないで、アルミニウムをモリブデンボートを用
いて５０ｎｍの膜厚でマグネシウム・銀合金膜の上に積
層して陰極４を完成させた。アルミニウム蒸着時の真空
度は１．５×１０-5Ｔｏｒｒ（約２．０×１０-3Ｐ
ａ）、蒸着時間は１分１５秒であった。以上のマグネシ
ウム・銀合金とアルミニウムの２層型陰極の蒸着時の基
板温度は室温に保持した。The above-described hole injection layer 3a 'and hole transport layer 3a
The substrate temperature when vacuum-depositing the electron transport layer 3b is room temperature
Held. Here, vapor deposition up to the electron transport layer 3b is performed.
Once removed element from the vacuum evaporation system to the atmosphere
2 mm wide stripes as a mask for cathode deposition
Make sure the shadow mask is orthogonal to the anode ITO stripe.
And placed in a separate vacuum evaporation system
Thus, the cathode 4 was formed as follows. First, magnesium
And a silver alloy electrode with a thickness of 55 nm by a binary simultaneous evaporation method.
Vapor deposition was performed so that Molybdenum boat used for evaporation
No, vacuum degree 1 × 10-FiveTorr (about 1.3 × 10 -3P
a), deposition time of 1 minute and 15 seconds, atoms of magnesium and silver
The run was performed with a ratio of 10: 1. Further on, the true
Do not break the sky, use aluminum for molybdenum boats
On the magnesium-silver alloy film with a thickness of 50 nm
To complete the cathode 4. Vacuum for aluminum deposition
The degree is 1.5 × 10-FiveTorr (about 2.0 × 10-3P
a), the deposition time was 1 minute and 15 seconds. Magnesi over
Base for deposition of a two-layer cathode made of aluminum-silver alloy and aluminum
The plate temperature was kept at room temperature.
【００６４】以上の様にして、２ｍｍ×２ｍｍのサイズ
の有機電界発光素子が得られた。この素子を陰極蒸着装
置から取り出した後、次に素子の封止を行った。先ず、
既述の有機層蒸着装置に再び上記素子を設置した後、こ
れまでに示したのと同様にして、化合物（Ｅ１）を膜厚
２００ｎｍで陰極４の上に積層して、保護層５とした。
この時の真空度は２×１０-6Ｔｏｒｒ（約２．７×１０
-4Ｐａ）、蒸着時間は６分１０秒で、基板温度は室温で
あった。素子を上記装置より大気中に取り出して、窒素
グローブボックス中に入れて実施例１と同様の方法で封
止を行った。As described above, an organic electroluminescent device having a size of 2 mm × 2 mm was obtained. After removing the device from the cathode vapor deposition device, the device was sealed. First,
After installing the above element again in the organic layer vapor deposition apparatus described above, the compound (E1) was laminated on the cathode 4 in a thickness of 200 nm in the same manner as described above to form the protective layer 5. .
The degree of vacuum at this time is 2 × 10 −6 Torr (about 2.7 × 10 Torr).
-4 Pa), the deposition time was 6 minutes and 10 seconds, and the substrate temperature was room temperature. The device was taken out of the above device into the atmosphere, placed in a nitrogen glove box, and sealed in the same manner as in Example 1.
【００６５】この様にして得られた有機電界発光素子を
大気中において、定電流駆動で電流密度を１５ｍＡ／ｃ
ｍ2 として直流連続駆動させた。この時の初期輝度は３
７０ｃｄ／ｍ2 であった。駆動時の輝度の経時変化を図
７に示す。５７０時間連続駆動後のダークスポットは
０．１％未満であった。The organic electroluminescent device thus obtained was exposed to air at a constant current density of 15 mA / c in the atmosphere.
DC continuous drive was performed at m 2 . The initial luminance at this time is 3
It was 70 cd / m 2 . FIG. 7 shows a temporal change in luminance during driving. The dark spot after continuous driving for 570 hours was less than 0.1%.
【００６６】比較例２ 封止層６に用いる封止剤をシリコーンオイル（信越シリ
コーン社製、商品名ＫＦ−５４）中にシリカゲル粉末を
入れた封止剤に変えた他は実施例２と同様にして封止素
子を作製した。この素子を大気中において、定電流駆動
で電流密度を１５ｍＡ／ｃｍ2 として直流連続駆動させ
た。この時の初期輝度は３６０ｃｄ／ｍ 2 であった。駆
動時の輝度の経時変化を図７に示す。３３３時間駆動後
でダークスポットは５４％に達した。Comparative Example 2 The sealing agent used for the sealing layer 6 was silicone oil (Shin-Etsu Silicone).
Silica gel powder in Corn Corporation, trade name KF-54)
A sealing element was prepared in the same manner as in Example 2 except that the sealing agent was used.
A child was made. This element is driven at constant current in air
And the current density is 15 mA / cmTwo DC continuous drive as
Was. The initial luminance at this time is 360 cd / m. Two Met. Drive
FIG. 7 shows the change over time of the luminance during movement. After driving for 333 hours
And the dark spot reached 54%.
【００６７】比較例３ 保護層５を設けない他は実施例２と同様にして封止素子
を作製した。この素子を大気中において、定電流駆動で
電流密度を１５ｍＡ／ｃｍ2 として直流連続駆動させ
た。この時の初期輝度は２２０ｃｄ／ｍ2 であり、初期
の発光は不均一であった。駆動時の輝度の経時変化を図
７に示す。３１０時間駆動後でダークスポットは２９％
に達した。Comparative Example 3 A sealing element was produced in the same manner as in Example 2 except that the protective layer 5 was not provided. The device was continuously driven in the air at a constant current drive at a current density of 15 mA / cm 2 in the atmosphere. At this time, the initial luminance was 220 cd / m 2 , and the initial light emission was non-uniform. FIG. 7 shows a temporal change in luminance during driving. 29% dark spot after 310 hours drive
Reached.
【００６８】実施例３ 発光機能を有する電子輸送層３ｂを化合物（Ｅ１）をホ
ストとして、以下に示すルブレン（Ｄ１）Example 3 Using the compound (E1) as a host and the rubrene (D1) shown below as an electron transporting layer 3b having a light emitting function
【００６９】[0069]
【化５】 Embedded image
【００７０】をドープ色素として、２元同時蒸着により
形成した他は実施例２と同様にして封止素子を作製し
た。電子輸送層３ｂに含まれるルブレンの濃度は２．７
モル％であった。A sealing element was produced in the same manner as in Example 2, except that the element was formed by binary simultaneous vapor deposition as a doping dye. The concentration of rubrene contained in the electron transport layer 3b is 2.7
Mole%.
【００７１】この様にして得られた有機電界発光素子を
大気中において、定電流駆動で電流密度を１５ｍＡ／ｃ
ｍ2 として直流連続駆動させた。この時の初期輝度は５
３５ｃｄ／ｍ2 であった。駆動時の輝度の経時変化を図
８に示す。３８０時間駆動後のダークスポットは０．１
％未満であった。図８の輝度の低下速度から輝度の半減
時間は１０，０００時間程度が予想され、従来の有機Ｅ
Ｌ素子と比べて飛躍的な駆動寿命が達成された。電圧の
変化は初期の７．２Ｖに対して、３８０時間後で８．０
Ｖと１Ｖ以下の増加に抑制された。The organic electroluminescent device obtained as described above was driven in a constant current drive at a current density of 15 mA / c in air.
DC continuous drive was performed at m 2 . The initial luminance at this time is 5
It was 35 cd / m 2 . FIG. 8 shows a temporal change in luminance during driving. Dark spot after driving for 380 hours is 0.1
%. From the luminance decrease rate in FIG. 8, the luminance half-life is expected to be about 10,000 hours.
Dramatic drive life was achieved as compared with the L element. The voltage change was 8.0 V after 380 hours from the initial 7.2 V.
V and the increase was suppressed to 1 V or less.
【００７２】実施例４ 実施例３と同様にして作製した封止素子を小型環境試験
器（タバイエスペック社製ＳＨ２２０型）により、６０
℃−９０％ＲＨの条件で２４時間保存後の素子特性を測
定した。測定結果を保存前の特性とともに以下の表−１
に示す。Example 4 A sealing element manufactured in the same manner as in Example 3 was subjected to a compact environmental tester (Model SH220 manufactured by Tabai Espec Corp.) for 60 hours.
The device characteristics after storage for 24 hours under the conditions of ° C. and 90% RH were measured. Table 1 below shows the measurement results together with the characteristics before storage.
Shown in
【００７３】[0073]
【表２】 [Table 2]
【００７４】上記の環境試験で輝度および発光効率に劣
化はなく、ダークスポットの増加もみられず、本発明に
おける封止方法が高温高湿度下でも十分信頼性を有する
ことが示された。In the above environmental test, there was no deterioration in luminance and luminous efficiency, and no increase in dark spots was observed. This indicates that the sealing method of the present invention has sufficient reliability even under high temperature and high humidity.
【００７５】[0075]
【発明の効果】本発明の有機電界発光素子の封止方法に
よれば、特定の接着剤から成る封止層を有するために、
大気中での保存や駆動の際に安定した発光特性を示す封
止素子を得ることができる。従って、本発明による有機
電界発光素子はフラットパネル・ディスプレイ（例えば
ＯＡコンピュータ用や壁掛けテレビ）や面発光体として
の特徴を生かした光源（例えば、複写機の光源、液晶デ
ィスプレイや計器類のバックライト光源）、表示板、標
識灯への応用が考えられ、その技術的価値は大きいもの
である。According to the method for sealing an organic electroluminescent device of the present invention, since a sealing layer made of a specific adhesive is provided,
It is possible to obtain a sealing element exhibiting stable light emission characteristics during storage or driving in the air. Accordingly, the organic electroluminescent device according to the present invention can be used as a flat panel display (for example, for an OA computer or a wall-mounted television) or a light source utilizing the characteristics of a surface light emitter (for example, a light source of a copier, a backlight of a liquid crystal display or an instrument). It can be applied to light sources, display boards, and marker lights, and its technical value is great.
【図１】有機電界発光素子の一例を示した模式断面図。FIG. 1 is a schematic cross-sectional view showing an example of an organic electroluminescent device.
【図２】有機電界発光素子の別の例を示した模式断面
図。FIG. 2 is a schematic sectional view showing another example of the organic electroluminescent device.
【図３】有機電界発光素子の更に別の例を示した模式断
面図。FIG. 3 is a schematic sectional view showing still another example of the organic electroluminescent element.
【図４】本発明における有機電界発光素子の封止方法の
一例を示した模式図。FIG. 4 is a schematic view showing an example of a method for sealing an organic electroluminescent element according to the present invention.
【図５】実施例１及び比較例１における有機電界発光素
子の大気中保存時の発光輝度（初期輝度を１とした）の
経時変化を示すグラフ。FIG. 5 is a graph showing the change over time of the light emission luminance (assuming the initial luminance is 1) of the organic electroluminescent elements in Example 1 and Comparative Example 1 during storage in air.
【図６】実施例１及び比較例１における有機電界発光素
子の大気中保存時のダークスポットの経時変化を示すグ
ラフ。FIG. 6 is a graph showing a change over time of a dark spot of the organic electroluminescent element in Example 1 and Comparative Example 1 when stored in the air.
【図７】実施例２、比較例２及び比較例３における有機
電界発光素子の大気中駆動時の発光輝度（初期輝度を１
とした）の経時変化を示すグラフ。FIG. 7 shows the emission luminance of an organic electroluminescent device in Example 2, Comparative Example 2 and Comparative Example 3 when driven in air (initial luminance is 1).
) Is a graph showing the change over time.
【図８】実施例３における有機電界発光素子の大気中駆
動時の発光輝度（初期輝度を１とした）の経時変化を示
すグラフ。FIG. 8 is a graph showing a change with time in emission luminance (assuming initial luminance is 1) of the organic electroluminescent element in Example 3 when driven in air.
１ 基板 ２ 陽極 ３ 有機発光層 ４ 陰極 ３ａ 正孔輸送層 ３ｂ 電子輸送層 ３ａ’ 正孔注入層 ５ 保護層 ６ 封止層 ７ 外気遮断材層 ８ 接着部 DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Organic light emitting layer 4 Cathode 3a Hole transport layer 3b Electron transport layer 3a 'Hole injection layer 5 Protective layer 6 Sealing layer 7 Outside air-blocking material layer 8 Adhesion part
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H05B 33/04 Continuation of front page (58) Field surveyed (Int.Cl. 7 , DB name) H05B 33/04
Claims (7)
積層され、該積層物の外表面に、内側から順に保護層、
封止層、外気遮断材層が形成されてなる有機電界発光素
子であって、前記封止層が下記（イ）、（ロ）、（ハ）
の条件を満たす樹脂を主成分とすることを特徴とする有
機電界発光素子。 （イ）ＪＩＳ Ｋ ６９１１に規定される伸びが１００
％以上。 （ロ）ＪＩＳ Ｋ ６３０１に規定されるショアーＡ硬
度が２０以上。 （ハ）ガラス転移点が−４０℃以下で、−４０〜＋１０
０℃の温度範囲でゴム状弾性を示す。An anode, an organic light emitting layer and a cathode are laminated on a substrate, and a protective layer is formed on the outer surface of the laminate in order from the inside,
An organic electroluminescent device comprising a sealing layer and an outside air-blocking material layer, wherein the sealing layer has the following (a), (b), and (c)
An organic electroluminescent device comprising, as a main component, a resin satisfying the following conditions. (B) The elongation specified in JIS K 6911 is 100
%that's all. (B) Shore A hardness specified in JIS K6301 is 20 or more. (C) a glass transition point of −40 ° C. or lower and −40 to +10
It exhibits rubbery elasticity in the temperature range of 0 ° C.
樹脂が変性シリコーン系弾性接着剤である請求項１に記
載の有機電界発光素子。2. The organic electroluminescent device according to claim 1, wherein the resin satisfying the conditions (a), (b) and (c) is a modified silicone elastic adhesive.
塩化カルシウム、活性炭、ナイロン及びポリビニルアル
コールから選ばれる少なくとも一つの吸湿剤が含有され
ている請求項１又は２に記載の有機電界発光素子。3. The method according to claim 1, wherein the sealing layer comprises silica gel, zeolite,
The organic electroluminescent device according to claim 1, further comprising at least one hygroscopic agent selected from calcium chloride, activated carbon, nylon, and polyvinyl alcohol.
たは電気絶縁性高分子から成る請求項１〜３のいずれか
１つに記載の有機電界発光素子。4. The organic electroluminescent device according to claim 1, wherein the outside air blocking material layer is made of an electrically insulating glass or an electrically insulating polymer.
より小さい請求項１〜４のいずれか１つに記載の有機電
界発光素子。5. The organic electroluminescent device according to claim 1, wherein the thickness of the cathode is smaller than the thickness of the organic light emitting layer.
り、かつ、その表面粗さが１０ｎｍ以下である請求項１
〜５のいずれか１つに記載の有機電界発光素子。6. The anode according to claim 1, wherein the anode is indium tin oxide and has a surface roughness of 10 nm or less.
6. The organic electroluminescent device according to any one of items 1 to 5,
積層し、該積層物の外表面に、保護層を設けた後、下記
（イ）、（ロ）、（ハ）の条件を満たす樹脂を主成分と
する封止層を形成し、前記封止層の外側に外気遮断材層
をさらに設けることを特徴とする請求項１〜６のいずれ
か１つに記載の有機電界発光素子の製造方法。 （イ）ＪＩＳ Ｋ ６９１１に規定される伸びが１００
％以上。 （ロ）ＪＩＳ Ｋ ６３０１に規定されるショアーＡ硬
度が２０以上。 （ハ）ガラス転移点が−４０℃以下で、−４０〜＋１０
０℃の温度範囲でゴム状弾性を示す。7. An anode, an organic light-emitting layer and a cathode are laminated on a substrate, and a protective layer is provided on the outer surface of the laminate, and then the following conditions (A), (B) and (C) are performed. The organic electroluminescent element according to claim 1, further comprising: forming a sealing layer mainly containing a resin to be filled, and further providing an outside air blocking material layer outside the sealing layer. Manufacturing method. (B) The elongation specified in JIS K 6911 is 100
%that's all. (B) Shore A hardness specified in JIS K6301 is 20 or more. (C) a glass transition point of −40 ° C. or lower and −40 to +10
It exhibits rubbery elasticity in the temperature range of 0 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4209695A JP3334408B2 (en) | 1995-03-01 | 1995-03-01 | Organic electroluminescent device and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4209695A JP3334408B2 (en) | 1995-03-01 | 1995-03-01 | Organic electroluminescent device and method of manufacturing the same |
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| Publication Number | Publication Date |
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| JP3334408B2 true JP3334408B2 (en) | 2002-10-15 |
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-
1995
- 1995-03-01 JP JP4209695A patent/JP3334408B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 有機発光素子の発光特性に及ぼすＩＴＯ基板の影響，第５２回応用物理学会学術講演会予稿集，１０Ｐ−Ｓ−９，１０９４ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08236271A (en) | 1996-09-13 |
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