JPH06116552A - Organic electroluminescent element - Google Patents
Organic electroluminescent elementInfo
- Publication number
- JPH06116552A JPH06116552A JP4264627A JP26462792A JPH06116552A JP H06116552 A JPH06116552 A JP H06116552A JP 4264627 A JP4264627 A JP 4264627A JP 26462792 A JP26462792 A JP 26462792A JP H06116552 A JPH06116552 A JP H06116552A
- Authority
- JP
- Japan
- Prior art keywords
- transport layer
- hole transport
- layer
- light emitting
- organic electroluminescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機色素より成る発光
層を備えた有機電界発光素子に係り、特に、１０Ｖ前後
の極低電圧の条件下でも高輝度でかつ長期に亘り安定し
て発光する有機電界発光素子の改良に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device provided with a light emitting layer made of an organic dye, and in particular, emits light with high brightness and for a long period of time even under an extremely low voltage of about 10V. The present invention relates to an improvement of the organic electroluminescence device.
【０００２】[0002]
【従来の技術】電界発光素子は従来からよく知られてお
り、一般には２つの電極間に正孔輸送層と発光層とを備
え、正孔輸送層を通じて陽極電極から供給された正孔と
他方の陰極電極から供給された電子とが上記発光層と正
孔輸送層の界面で再結合して一重項励起子を生成し上記
発光層が発光するものである。2. Description of the Related Art Electroluminescent devices are well known in the art, and generally include a hole transport layer and a light emitting layer between two electrodes, and holes supplied from an anode electrode through the hole transport layer and the other. The electrons supplied from the cathode electrode are recombined at the interface between the light emitting layer and the hole transport layer to generate singlet excitons, and the light emitting layer emits light.
【０００３】そして、上記電界発光素子の発光効率を高
めるためには、電子や正孔等の電荷注入効率、電荷輸送
効率、一重項励起子の生成確率、及び、一重項励起子の
発光遷移確率等を高めることが重要であり、例えば、陰
極電極から電子を適切に発光層に輸送すると共に、正孔
輸送層から輸送された正孔が一重項励起子生成に関与せ
ず発光層を透過して陰極へ移動することを防止する電子
輸送層を上記発光層と陰極電極の間に設け、一重項励起
子の生成確率を向上させて発光効率を高めた電界発光素
子も開発されている。In order to increase the luminous efficiency of the electroluminescent device, the charge injection efficiency of electrons, holes, etc., the charge transport efficiency, the generation probability of singlet excitons, and the emission transition probability of singlet excitons. Etc. is important, and for example, while appropriately transporting electrons from the cathode electrode to the light emitting layer, the holes transported from the hole transporting layer pass through the light emitting layer without participating in singlet exciton generation. Electroluminescent devices have also been developed in which an electron transport layer for preventing the transfer of electrons to the cathode is provided between the light emitting layer and the cathode electrode to improve the probability of generation of singlet excitons and increase the luminous efficiency.
【０００４】ところで、このような電界発光素子として
は、従来、発光層に硫化セレンや硫化亜鉛等の無機系蛍
光体を用いた無機系の電界発光素子が一般的であった
が、近年、発光層として有機色素を利用した有機電界発
光素子が提案されている。By the way, as such an electroluminescent element, conventionally, an inorganic electroluminescent element using an inorganic phosphor such as selenium sulfide or zinc sulfide in a light emitting layer has been generally used. Organic electroluminescent devices using organic dyes as layers have been proposed.
【０００５】例えば、特開昭５９−１９４３９３号に記
載された有機電界発光素子は、陽極上に、順次、正孔輸
送層、有機色素より成る発光層、陰極を設けて構成さ
れ、両電極間に２５Ｖ以下の低電圧を印加した場合に少
なくとも９×１０-5（Ｗ／Ｗ）に及ぶ電力転換効率（入
力に対する出力の比で定義されシステムの駆動電圧の関
数）をもって発光するものであった。For example, the organic electroluminescent device described in JP-A-59-194393 is constructed by sequentially providing a hole transporting layer, a light emitting layer made of an organic dye, and a cathode on an anode. When a low voltage of 25 V or less is applied to the device, it emits light with a power conversion efficiency (defined as a ratio of output to input and a function of system driving voltage) reaching at least 9 × 10 -5 (W / W). .
【０００６】また、特開平２−２５５７８９号公報にお
いては上記発光層にナフタレン誘導体を適用することに
より、また、特開平２−２２３１８８号公報では正孔輸
送材料と発光材料の混合物層若しくは電子輸送材料と発
光材料の混合物層を適用することにより発光効率や発光
輝度などを改善した有機電界発光素子が開示されてい
る。Further, in JP-A-2-255789, a naphthalene derivative is applied to the light emitting layer, and in JP-A-2-223188, a mixture layer of a hole transporting material and a light emitting material or an electron transporting material. There is disclosed an organic electroluminescent device having improved luminous efficiency, luminous brightness and the like by applying a mixture layer of a luminous material and a luminous material.
【０００７】[0007]
【発明が解決しようとする課題】ところで、これ等公報
に記載された有機電界発光素子においては、その発光輝
度の初期値としてはいずれもほぼ十分な値を示している
が発光輝度の安定性や発光寿命の点で十分な性能を示す
ものは未だ得られていなかった。By the way, in the organic electroluminescent elements described in these publications, the initial value of the emission brightness is almost sufficient, but the stability of the emission brightness and the The one showing sufficient performance in terms of emission life has not yet been obtained.
【０００８】そして、この原因は上記有機電界発光素子
の一部を構成する正孔輸送層の膜厚が本来の正孔輸送機
能を発現するために必要な膜厚よりも厚く設定されてい
ることにあった。すなわち、上記正孔輸送層に適用され
ている従来の材料では、その膜厚を薄く設定するとピン
ホールを回避することが困難になるため本来の正孔輸送
機能を発現するために必要な膜厚より厚く設定せざるを
得なかった。従って、その分、正孔輸送層の抵抗値が高
くなるため駆動時における上記正孔輸送層からの発熱が
避けられなくなる。The cause of this is that the thickness of the hole transport layer forming a part of the organic electroluminescence device is set to be thicker than the thickness necessary for exhibiting the original hole transport function. There was That is, in the conventional material applied to the hole transport layer, it is difficult to avoid pinholes when the film thickness is set to be small, so that the film thickness required for exhibiting the original hole transport function. I had to set it thicker. Therefore, the resistance value of the hole transport layer becomes higher accordingly, so that heat generation from the hole transport layer during driving cannot be avoided.
【０００９】他方、上記正孔輸送層や発光層等の製膜手
段としては、通常、蒸着法や湿式法が適用されているた
め、製膜されたこれ等正孔輸送層や発光層の膜構造はア
モルファスである場合がほとんどであった。On the other hand, as the film forming means for the hole transporting layer, the light emitting layer and the like, the vapor deposition method and the wet method are usually applied. In most cases, the structure was amorphous.
【００１０】このため、実用に値する輝度を得る程度の
印加電圧で生ずる上記正孔輸送層からの発熱に起因し
て、構成材料である有機化合物が容易に動いてしまい最
適な膜構造を維持できなくなると共に上記有機化合物が
熱的ダメージを受ける弊害があった。Therefore, the organic compound as a constituent material easily moves due to the heat generation from the hole transport layer generated by the applied voltage at the level of obtaining practically usable brightness, and the optimum film structure can be maintained. When the organic compound disappears, the organic compound has a harmful effect of being thermally damaged.
【００１１】そして、これ等のことが原因となって電荷
の注入及び輸送効率が低下すると共に抵抗値が増大し、
駆動電圧の上昇及びジュール発熱の増大等の問題を引き
起こし、発光効率の低下や発光寿命の低下をもたらして
いた。Due to these factors, the charge injection and transport efficiency is lowered and the resistance value is increased.
This causes problems such as an increase in driving voltage and Joule heat generation, resulting in a decrease in light emission efficiency and a decrease in light emission life.
【００１２】特に、上記正孔輸送層や発光層等の製膜手
段にキャスティング法やスピンコート法などの湿式製膜
法が適用された場合、正孔輸送層を構成する製膜材料に
はピンホールを回避するための結着材が混入されている
ため電気抵抗値が更に高くなり、上記弊害が更に顕著に
なる問題点があった。In particular, when a wet film forming method such as a casting method or a spin coating method is applied to the film forming means such as the hole transporting layer or the light emitting layer, the film forming material forming the hole transporting layer is a pin. Since the binder for avoiding the holes is mixed, the electric resistance value is further increased, and there is a problem that the above-mentioned adverse effect becomes more remarkable.
【００１３】本発明はこのような問題点に着目してなさ
れたもので、その課題とするところは、低電圧の条件下
においても高輝度でかつ長期に亘り安定して発光する有
機電界発光素子を提供することにある。The present invention has been made by paying attention to such a problem, and an object thereof is to obtain an organic electroluminescence device which emits light with high brightness and stable for a long period of time even under a condition of low voltage. To provide.
【００１４】[0014]
【課題を解決するための手段】この様な技術的背景の
下、本発明者等が低電圧で高輝度に発光し得る有機色素
について鋭意検討した結果、ある特定の２種類の化合物
から成る混合物を用いて上記正孔輸送層を構成した場
合、この正孔輸送層の膜厚について正孔輸送機能を発現
するために必要な最低限の膜厚に設定してもピンホール
が生じないことを見出だし本発明を完成するに至ったも
のである。Under the above technical background, the inventors of the present invention have made diligent studies on organic dyes capable of emitting light with high brightness at low voltage, and as a result, a mixture of two specific compounds. When the hole-transporting layer is formed by using, it is confirmed that pinholes do not occur even if the thickness of the hole-transporting layer is set to the minimum film thickness required to exhibit the hole-transporting function. The present invention has been completed and the present invention has been completed.
【００１５】すなわち請求項１に係る発明は、２つの電
極間に、正孔輸送層と有機色素より成る発光層とを備
え、又は、正孔輸送層と電子輸送層及びこれ等に挟まれ
た有機色素より成る発光層とを備える有機電界発光素子
を前提とし、上記正孔輸送層が下記一般式（１）で示さ
れるいずれか一方の化合物と下記一般式（２）で示され
る化合物との混合物により構成されていることを特徴と
するものである。That is, the invention according to claim 1 is provided with a hole transport layer and a light emitting layer made of an organic dye between two electrodes, or is sandwiched between a hole transport layer and an electron transport layer and these. Based on the premise of an organic electroluminescent device including a light emitting layer made of an organic dye, the hole transport layer comprises one of the compounds represented by the following general formula (1) and the compound represented by the following general formula (2). It is characterized by being composed of a mixture.
【００１６】[0016]
【化３】 [Chemical 3]
【化４】 本発明に係る有機電界発光素子においては、従来と同様
に、上記発光層を正孔輸送層と共に２つの電極で挟み、
この２つの電極から注入される正孔と電子を正孔輸送層
と発光層の界面で結合させて発光層を発光させる。従っ
て、この２つの電極のうち正孔輸送層側に設けられる電
極は陽極用電極であり、他方、発光層側に配置される電
極は陰極用電極である。[Chemical 4] In the organic electroluminescent device according to the present invention, as in the conventional case, the light emitting layer is sandwiched between two electrodes together with the hole transport layer,
The holes and electrons injected from the two electrodes are combined at the interface between the hole transport layer and the light emitting layer to cause the light emitting layer to emit light. Therefore, of these two electrodes, the electrode provided on the hole transport layer side is the electrode for the anode, while the electrode arranged on the light emitting layer side is the electrode for the cathode.
【００１７】また、発光層から生じる蛍光を外部へ射出
するため、陽極側、陰極側のどちらでもよいが光を取出
す側については、基板材料、電極材料、電荷移動材料共
に発光波長が透過し得る透明性を必要とする。Further, since the fluorescence generated from the light emitting layer is emitted to the outside, either the anode side or the cathode side may be used, but the emission wavelength can be transmitted to both the substrate material, the electrode material and the charge transfer material on the light extraction side. Needs transparency.
【００１８】上記基板材料としては、例えば、ソーダラ
イムガラスや硼珪酸ガラス等のガラス基板、シリコンウ
エハー若しくはポリカーボネート、アクリル、エポキシ
等の合成樹脂基板等が挙げられる。Examples of the substrate material include glass substrates such as soda lime glass and borosilicate glass, silicon wafers or synthetic resin substrates such as polycarbonate, acryl and epoxy.
【００１９】また、上記陽極用電極としては正孔を効率
よく注入できるものが好ましく、例えば、ＳｎＯ2 、Ｉ
ｎＯ2 、若しくはＩＴＯ等の透明電極、あるいは金又は
ニッケルから成る半透明電極等従来公知の電極材料がい
ずれも適用可能である。Further, the above-mentioned anode electrode is preferably one capable of efficiently injecting holes, and examples thereof include SnO 2 and I.
Any conventionally known electrode material such as a transparent electrode made of nO 2 or ITO, or a semitransparent electrode made of gold or nickel can be applied.
【００２０】また、陰極用電極としては電子を効率よく
注入できる金属が好ましく、Ｍｇ、Ａｌ、Ａｇ、Ｉｎ、
Ｌｉ、Ｎａなどに代表される仕事関数の小さな金属であ
ればいずれも使用可能であり、真空蒸着法やスパッタリ
ング法により３０ｎｍ以上の膜厚に製膜形成されるもの
が好ましい。As the cathode electrode, a metal capable of efficiently injecting electrons is preferable, and Mg, Al, Ag, In,
Any metal having a small work function, such as Li or Na, can be used, and those formed into a film thickness of 30 nm or more by a vacuum vapor deposition method or a sputtering method are preferable.
【００２１】一方、正孔輸送層は、電場を与えられた電
極間において陽極用電極からの正孔を適切に効率良く発
光層へ伝達することができ、かつ、機能発現に必要な最
低限の膜厚でもピンホールを生ずることなく製膜可能な
低抵抗化合物により構成することができる。On the other hand, the hole transport layer can appropriately and efficiently transfer the holes from the anode electrode to the light emitting layer between the electrodes to which an electric field is applied, and has the minimum amount necessary for exhibiting the function. It can be made of a low resistance compound capable of forming a film without causing pinholes even in the film thickness.
【００２２】そして、本発明においては下記一般式
（１）で示されるいずれか一方の化合物と下記一般式
（２）で示される化合物との混合物が適用され、好まし
くは真空蒸着法等の方法により５〜６０ｎｍの膜厚に形
成される。In the present invention, a mixture of any one compound represented by the following general formula (1) and a compound represented by the following general formula (2) is applied, preferably by a method such as a vacuum deposition method. It is formed to a film thickness of 5 to 60 nm.
【００２３】[0023]
【化５】 [Chemical 5]
【化６】 また、上記発光層は可視光域に強い蛍光を示し、かつ、
製膜性の良い有機化合物なら任意の材料が適用できる。
例えば、ピレン、ペリレン、ペリレン誘導体類、ペリノ
ン誘導体類、アントラセン、金属フタロシアニン類、無
金属フタロシアニン類、ポルフィリン類等、従来公知の
材料が適用可能であり、真空蒸着法等により３〜１００
ｎｍの膜厚に製膜形成されたものが好ましい。[Chemical 6] Further, the light emitting layer exhibits strong fluorescence in the visible light region, and
Any material can be applied as long as it is an organic compound having a good film forming property.
For example, conventionally known materials such as pyrene, perylene, perylene derivatives, perinone derivatives, anthracene, metal phthalocyanines, metal-free phthalocyanines, porphyrins, etc. can be applied, and 3 to 100 by a vacuum vapor deposition method or the like.
It is preferably formed into a film having a thickness of nm.
【００２４】また、発光層から陰極用電極に正孔が移動
することを防止すると共に陰極用電極から発光層へ電子
を適切に注入して一重項励起子の生成確率を向上するた
め、発光層と陰極用電極の間に電子輸送層を設けること
ができる。このような電子輸送層としては、電場を与え
られた電極間において、陽極からの正孔をブロックし、
陰極からの電子を適切に陰極側へ伝達することができる
化合物により形成することができる。Further, holes are prevented from moving from the light emitting layer to the cathode electrode, and electrons are appropriately injected from the cathode electrode to the light emitting layer to improve the probability of generation of singlet excitons. An electron transport layer can be provided between the cathode electrode and the cathode electrode. Such an electron-transporting layer blocks holes from the anode between electrodes to which an electric field is applied,
It can be formed by a compound that can appropriately transfer electrons from the cathode to the cathode side.
【００２５】この電子輸送層に適用できる無機化合物と
しては、Ｐ（燐）がドーピングされたｎ型のアモルファ
スシリコン薄膜、若しくはＣｄＳ（ｎ型）、ＣｄＳｅ
（ｎ型）、ＺｎＳ（ｎ型）、ＺｎＳｅ（ｎ型）等の化合
物半導体薄膜が例示できる。As an inorganic compound applicable to this electron transport layer, an n-type amorphous silicon thin film doped with P (phosphorus), or CdS (n-type) or CdSe.
Examples thereof include compound semiconductor thin films such as (n-type), ZnS (n-type), and ZnSe (n-type).
【００２６】他方、有機化合物としては、例えば、アミ
ノ基又はその誘導体を有するようなトリフェニルメタ
ン、キサンテン、アクリジン、アジン、チアジン、チア
ゾ−ル、オキサジン、アゾ等の各種染料及び顔料、ペリ
ノン系顔料、ペリレン系顔料、シアニン色素、２，４，
７−トリニトロフルオレノン、テトラシアノキノジメタ
ン、テトラシアノエチレンなどが適用できる。On the other hand, examples of the organic compound include various dyes and pigments such as triphenylmethane, xanthene, acridine, azine, thiazine, thiazole, oxazine and azo having an amino group or a derivative thereof, and a perinone-based pigment. , Perylene pigments, cyanine dyes, 2, 4,
7-trinitrofluorenone, tetracyanoquinodimethane, tetracyanoethylene and the like can be applied.
【００２７】そして、好ましくは真空蒸着法等の方法に
より５〜７０ｎｍの膜厚に形成される。Then, it is preferably formed to a film thickness of 5 to 70 nm by a method such as a vacuum vapor deposition method.
【００２８】[0028]
【作用】請求項１に係る発明によれば、上記一般式
（１）で示されるいずれか一方の化合物と上記一般式
（２）で示される化合物との混合物により正孔輸送層が
構成されているため、機能発現に必要な最低限の膜厚に
設定してもピンホールを生ずることなく正孔輸送層が形
成され、かつ、正孔輸送効率を向上させることも可能と
なる。According to the first aspect of the present invention, the hole transport layer is constituted by a mixture of any one of the compounds represented by the general formula (1) and the compound represented by the general formula (2). Therefore, even if the film thickness is set to the minimum necessary for exhibiting the function, the hole transport layer is formed without generating pinholes, and the hole transport efficiency can be improved.
【００２９】従って、１０Ｖ前後という極低電圧の条件
下でも高輝度でかつ長期に亘り安定して発光する有機電
界発光素子を提供することが可能となる。Therefore, it is possible to provide an organic electroluminescence device which emits light with high brightness and stable for a long period of time even under an extremely low voltage of about 10V.
【００３０】[0030]
【実施例】以下、本発明を実施例に従って更に詳細に説
明する。The present invention will be described in more detail below with reference to examples.
【００３１】［実施例１］この実施例に係る有機電界発
光素子は、図１に示すように松崎真空（株）製の硼珪酸
ガラス基板１と、このガラス基板１上に順に形成された
ＩＴＯ膜から成る陽極用透明電極２、正孔輸送層３、発
光層４、及び、金属マグネシウムから成る陰極用金属電
極６とでその主要部が構成されており、かつ、この素子
面積の大きさは０．２５ｃｍ2 （５ｍｍ×５ｍｍ）に設
定されている。Example 1 As shown in FIG. 1, the organic electroluminescent device according to this example has a borosilicate glass substrate 1 manufactured by Matsuzaki Vacuum Co., Ltd., and an ITO layer formed on the glass substrate 1 in this order. The anode transparent electrode 2 made of a film, the hole transport layer 3, the light emitting layer 4, and the cathode metal electrode 6 made of magnesium metal constitute the main part, and the size of the element area is It is set to 0.25 cm 2 (5 mm × 5 mm).
【００３２】そして、上記正孔輸送層３は下記一般式
（３）で示された化合物と下記一般式（２）で示された
化合物との混合物により構成され、かつ、上記発光層４
は下記一般式（４）で示された化合物により構成されて
いる。The hole transport layer 3 is composed of a mixture of a compound represented by the following general formula (3) and a compound represented by the following general formula (2), and the light emitting layer 4 is
Is composed of a compound represented by the following general formula (4).
【００３３】[0033]
【化７】 [Chemical 7]
【化８】 [Chemical 8]
【化９】 尚、上記陽極用透明電極２を構成するＩＴＯ膜面内の抵
抗値の平均値は１０Ω／ｓｑ．、正孔輸送層３の膜厚は
５０ｎｍ、及び、発光層４の膜厚は７０ｎｍに設定され
ており、かつ、素子面積は陰極用金属電極６の面積によ
り規定した。[Chemical 9] The average value of the resistance values within the ITO film forming the transparent electrode 2 for the anode is 10 Ω / sq. The thickness of the hole transport layer 3 was set to 50 nm and the thickness of the light emitting layer 4 was set to 70 nm, and the element area was defined by the area of the metal electrode 6 for cathode.
【００３４】そして、図１に示すようにこの有機電界発
光素子の陽極用透明電極２と陰極用金属電極６の間に１
１Ｖの電圧を印加したところ、電流密度７８ｍＡ／ｃｍ
2 を示し、５７０ｎｍの波長にて輝度９００ｃｄ／ｍ2
の発光を示した。As shown in FIG. 1, 1 is provided between the transparent electrode 2 for the anode and the metal electrode 6 for the cathode of this organic electroluminescence device.
When a voltage of 1 V was applied, the current density was 78 mA / cm
2 indicates a luminance of 900 cd / m 2 at a wavelength of 570 nm.
Emission of light was shown.
【００３５】尚、この有機電界発光素子は以下のような
方法で製造されている。The organic electroluminescent device is manufactured by the following method.
【００３６】すなわち、まず松崎真空（株）製の硼珪酸
ガラス基板１表面のＩＴＯ膜を１５ｗｔ％の塩酸水溶液
で所望のパターンにエッチングして陽極用透明電極２を
形成し、かつ、純水で洗浄し、次いでエタノールの蒸気
洗浄を行い、クリーンオーブンで１００℃×１０Ｈｒの
条件で乾燥した。That is, first, the ITO film on the surface of the borosilicate glass substrate 1 manufactured by Matsuzaki Vacuum Co., Ltd. was etched in a desired pattern with a 15 wt% hydrochloric acid aqueous solution to form a transparent electrode 2 for an anode, and the pure electrode 2 was purified with pure water. It was washed, then steam-washed with ethanol, and dried in a clean oven under the conditions of 100 ° C. × 10 Hr.
【００３７】次に、上記正孔輸送層３は図２に示す真空
蒸着装置を使用し、ボート加熱法により形成した。Next, the hole transport layer 3 was formed by the boat heating method using the vacuum vapor deposition apparatus shown in FIG.
【００３８】すなわち、予めゾーンメルティング法によ
り精製した上記一般式（３）で示された化合物と一般式
（２）で示された化合物を使用し、これを熱電対付き加
熱ボード１１上に載置し、加熱して蒸発させ、膜厚及び
蒸発速度検出用水晶振動子１６により正孔輸送層３の膜
厚と蒸発速度を測定してシャッター１４の開口率を制御
しながらホルダー１０ａに固定されたガラス基板から成
る膜形成基板１０のＩＴＯ膜上に、一般式（３）で示さ
れた化合物と一般式（２）で示された化合物との混合物
から構成される正孔輸送層３を形成した。That is, the compound represented by the general formula (3) and the compound represented by the general formula (2) previously purified by the zone melting method are used and mounted on the heating board 11 with a thermocouple. The hole transporting layer 3 is fixed on the holder 10a while controlling the aperture ratio of the shutter 14 by measuring the film thickness and the evaporation rate of the hole transport layer 3 by the crystal oscillator 16 for detecting the film thickness and the evaporation rate. A hole transport layer 3 composed of a mixture of the compound represented by the general formula (3) and the compound represented by the general formula (2) is formed on the ITO film of the film forming substrate 10 including the glass substrate. did.
【００３９】尚、真空蒸着装置による共蒸着条件は以下
の通りである。The co-deposition conditions for the vacuum deposition apparatus are as follows.
【００４０】 背 圧：５．０×１０-7ｔｏｒｒ．以下 加熱 温度：１７０〜１９０℃ 蒸着レート：一般式（３）で示された化合物は０．３ｎ
ｍ／ｓｅｃ．一般式（２）で示された化合物は０．１ｎ
ｍ／ｓｅｃ． 膜 膜：５０ｎｍ 次に、この図２の真空蒸着装置の真空をブレークするこ
となく、同じ真空蒸着装置内でボート加熱法により発光
層４を形成した。Back pressure: 5.0 × 10 −7 torr. The following heating: Temperature: 170 to 190 ° C. Deposition rate: The compound represented by the general formula (3) is 0.3 n
m / sec. The compound represented by the general formula (2) is 0.1n
m / sec. Film Film: 50 nm Next, the light emitting layer 4 was formed by the boat heating method in the same vacuum evaporation system without breaking the vacuum of the vacuum evaporation system of FIG.
【００４１】すなわち、溶媒からの再結晶により精製し
た上記一般式（４）で示された化合物を蒸発源に用い、
これを熱電対付き加熱ボード１１上に載置して上記正孔
輸送層３の場合と同様に膜形成基板１０の正孔輸送層３
上に発光層４を形成した。That is, the compound represented by the above general formula (4) purified by recrystallization from a solvent is used as an evaporation source,
This is placed on the heating board 11 with a thermocouple and the hole transport layer 3 of the film forming substrate 10 is formed in the same manner as in the case of the hole transport layer 3.
The light emitting layer 4 was formed on top.
【００４２】真空蒸着条件は以下の通りである。The vacuum deposition conditions are as follows.
【００４３】 背 圧：５．０×１０-7ｔｏｒｒ．以下 加熱 温度：１８０〜２００℃ 蒸着レート：０．１ｎｍ／ｓｅｃ．〜１．０ｎｍ／ｓｅ
ｃ． 最後に、この図２の真空蒸着装置の真空をブレークする
ことなく、同じ真空蒸着装置内で電子線加熱法により陰
極用金属電極６を形成した。Back pressure: 5.0 × 10 −7 torr. The following heating temperature: 180 to 200 ° C. evaporation rate: 0.1 nm / sec. ~ 1.0 nm / se
c. Finally, the metal electrode 6 for the cathode was formed by the electron beam heating method in the same vacuum evaporation system without breaking the vacuum of the vacuum evaporation system of FIG.
【００４４】すなわち、純度９９．９９％のマグネシウ
ムをＢＮ製電子線加熱蒸着用るつぼ１２に載置し、電子
銃１３により加熱して蒸発させ、膜厚及び蒸発速度検出
用水晶振動子１７により陰極用金属電極６の膜厚と蒸発
速度を測定してシャッター１５の開口率を制御しなが
ら、膜形成基板１０の電子輸送層５上に陰極用金属電極
６を形成した。尚、図中、１８はマスクを示している。That is, magnesium having a purity of 99.99% is placed on a crucible 12 for electron beam heating vapor deposition made of BN, heated by an electron gun 13 to evaporate, and a cathode is produced by a crystal oscillator 17 for detecting a film thickness and an evaporation rate. The metal electrode 6 for cathode was formed on the electron transport layer 5 of the film formation substrate 10 while controlling the aperture ratio of the shutter 15 by measuring the film thickness and evaporation rate of the metal electrode 6 for use. In the figure, 18 indicates a mask.
【００４５】陰極用金属電極６の真空蒸着条件は以下の
通りである。The vacuum deposition conditions for the cathode metal electrode 6 are as follows.
【００４６】 背 圧：５．０×１０-7ｔｏｒｒ．以下 フィラメント電流：３０〜３５ｍＡ 蒸着レート：０．１ｎｍ／ｓｅｃ．〜１．０ｎｍ／ｓｅ
ｃ． ［実施例２］上記正孔輸送層３の構成材料として上記一
般式（２）で示される化合物と下記一般式（５）で示さ
れる化合物との混合物を適用したことを除き実施例１に
係る有機電界発光素子と略同一である。Back pressure: 5.0 × 10 −7 torr. Filament current: 30 to 35 mA Deposition rate: 0.1 nm / sec. ~ 1.0 nm / se
c. Example 2 Example 1 is applied except that a mixture of the compound represented by the general formula (2) and the compound represented by the following general formula (5) was applied as a constituent material of the hole transport layer 3. It is substantially the same as the organic electroluminescent device.
【００４７】[0047]
【化１０】 そして、図１に示す有機電界発光素子の陽極用透明電極
２と陰極用金属電極６の間に９．５Ｖの電圧を印加した
ところ、電流密度７０ｍＡ／ｃｍ2 を示し、５９０ｎｍ
の波長にて輝度９３０ｃｄ／ｍ2 の発光を示した。[Chemical 10] Then, when a voltage of 9.5 V was applied between the anode transparent electrode 2 and the cathode metal electrode 6 of the organic electroluminescent device shown in FIG. 1, a current density of 70 mA / cm 2 was shown and 590 nm.
The emission of light with a luminance of 930 cd / m 2 was exhibited at the wavelength of.
【００４８】［比較例］上記正孔輸送層３の構成材料と
して上記一般式（２）で示される化合物のみを適用した
ことを除き実施例１に係る有機電界発光素子と略同一で
ある。[Comparative Example] The organic electroluminescent device of Example 1 is substantially the same as the organic electroluminescent device of Example 1 except that only the compound represented by the general formula (2) is applied as a constituent material of the hole transport layer 3.
【００４９】尚、真空蒸着条件は以下の通りである。The vacuum deposition conditions are as follows.
【００５０】蒸着レート：０．３ｎｍ／ｓｅｃ． 膜 膜：６０ｎｍ そして、実施例と同様に、図１に示された有機電界発光
素子の陽極用透明電極２と陰極用金属電極６の間に１４
Ｖの電圧を印加したところ、電流密度４２ｍＡ／ｃｍ2
を示すと共に５２０ｎｍの波長にて輝度５００ｃｄ／ｍ
2 の発光を示しており、実施例に係る有機電界発光素子
より劣っていた。Deposition rate: 0.3 nm / sec. Film Film: 60 nm And, as in the example, 14 is provided between the anode transparent electrode 2 and the cathode metal electrode 6 of the organic electroluminescence device shown in FIG.
When a voltage of V was applied, the current density was 42 mA / cm 2
And a luminance of 500 cd / m at a wavelength of 520 nm.
2 shows light emission, which was inferior to that of the organic electroluminescent device according to the example.
【００５１】[0051]
【発明の効果】請求項１に係る発明によれば、機能発現
に必要な最低限の膜厚に設定してもピンホールを生ずる
ことなく正孔輸送層が形成され、かつ、正孔輸送効率を
向上させることも可能となる。According to the first aspect of the present invention, the hole transport layer is formed without generating pinholes even if the film thickness is set to the minimum necessary for exhibiting the function, and the hole transport efficiency is improved. It is also possible to improve.
【００５２】従って、１０Ｖ前後という極低電圧の条件
下でも高輝度でかつ長期に亘り安定して発光する有機電
界発光素子を提供できる効果を有している。Therefore, there is an effect that it is possible to provide an organic electroluminescence device which emits light with high brightness and stable for a long period of time even under an extremely low voltage of about 10V.
【図１】実施例に係る有機電界発光素子の断面説明図。FIG. 1 is an explanatory cross-sectional view of an organic electroluminescence device according to an example.
【図２】実施例において使用した真空蒸着装置の説明
図。FIG. 2 is an explanatory diagram of a vacuum vapor deposition device used in the examples.
１ ガラス基板 ２ 陽極用透明電極 ３ 正孔輸送層 ４ 発光層 ６ 陰極用金属電極 1 Glass substrate 2 Transparent electrode for anode 3 Hole transport layer 4 Light emitting layer 6 Metal electrode for cathode
Claims (1)
り成る発光層とを備え、又は、正孔輸送層と電子輸送層
及びこれ等に挟まれた有機色素より成る発光層とを備え
る有機電界発光素子において、 上記正孔輸送層が下記一般式（１）で示されるいずれか
一方の化合物と下記一般式（２）で示される化合物との
混合物により構成されていることを特徴とする有機電界
発光素子。 【化１】 【化２】 1. A hole transporting layer and a light emitting layer made of an organic dye are provided between two electrodes, or a light emitting layer made of an organic dye sandwiched between the hole transporting layer and the electron transporting layer. In the organic electroluminescent device including :, the hole transport layer is composed of a mixture of any one compound represented by the following general formula (1) and a compound represented by the following general formula (2). And an organic electroluminescent device. [Chemical 1] [Chemical 2]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4264627A JPH06116552A (en) | 1992-10-02 | 1992-10-02 | Organic electroluminescent element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4264627A JPH06116552A (en) | 1992-10-02 | 1992-10-02 | Organic electroluminescent element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06116552A true JPH06116552A (en) | 1994-04-26 |
Family
ID=17405971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4264627A Pending JPH06116552A (en) | 1992-10-02 | 1992-10-02 | Organic electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06116552A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635308A (en) * | 1994-04-26 | 1997-06-03 | Tdk Corporation | Phenylanthracene derivative and organic EL element |
| JP2001034231A (en) * | 1999-07-22 | 2001-02-09 | Seiko Epson Corp | El display device |
| US6555840B1 (en) * | 1999-02-16 | 2003-04-29 | Sharp Kabushiki Kaisha | Charge-transport structures |
| WO2004078872A3 (en) * | 2003-03-05 | 2004-12-16 | Lg Electronics Inc | Organic electroluminescent device |
| JP2006114544A (en) * | 2004-10-12 | 2006-04-27 | Chisso Corp | Organic electroluminescence element |
| JP2010006811A (en) * | 2008-06-24 | 2010-01-14 | Gracel Display Inc | New organic electroluminescent compound and organic electroluminescent device using the same |
| US8674494B2 (en) | 2011-08-31 | 2014-03-18 | Samsung Electronics Co., Ltd. | Semiconductor package having supporting plate and method of forming the same |
-
1992
- 1992-10-02 JP JP4264627A patent/JPH06116552A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635308A (en) * | 1994-04-26 | 1997-06-03 | Tdk Corporation | Phenylanthracene derivative and organic EL element |
| US6555840B1 (en) * | 1999-02-16 | 2003-04-29 | Sharp Kabushiki Kaisha | Charge-transport structures |
| JP2001034231A (en) * | 1999-07-22 | 2001-02-09 | Seiko Epson Corp | El display device |
| WO2004078872A3 (en) * | 2003-03-05 | 2004-12-16 | Lg Electronics Inc | Organic electroluminescent device |
| US7651788B2 (en) | 2003-03-05 | 2010-01-26 | Lg Display Co., Ltd. | Organic electroluminescent device |
| JP2006114544A (en) * | 2004-10-12 | 2006-04-27 | Chisso Corp | Organic electroluminescence element |
| JP2010006811A (en) * | 2008-06-24 | 2010-01-14 | Gracel Display Inc | New organic electroluminescent compound and organic electroluminescent device using the same |
| EP2147962A1 (en) * | 2008-06-24 | 2010-01-27 | Gracel Display Inc. | Azaanthracene-derivatives and organic electroluminescent device using the same |
| US8674494B2 (en) | 2011-08-31 | 2014-03-18 | Samsung Electronics Co., Ltd. | Semiconductor package having supporting plate and method of forming the same |
| US9412720B2 (en) | 2011-08-31 | 2016-08-09 | Samsung Electronics Co., Ltd. | Semiconductor package having supporting plate and method of forming the same |
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