JP4343653B2 - Organic light emitting device having metal borate or metal organic boride - Google Patents
Organic light emitting device having metal borate or metal organic boride Download PDFInfo
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- JP4343653B2 JP4343653B2 JP2003380076A JP2003380076A JP4343653B2 JP 4343653 B2 JP4343653 B2 JP 4343653B2 JP 2003380076 A JP2003380076 A JP 2003380076A JP 2003380076 A JP2003380076 A JP 2003380076A JP 4343653 B2 JP4343653 B2 JP 4343653B2
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- metal
- organic
- light emitting
- cathode
- layer
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- 239000002184 metal Substances 0.000 title claims description 86
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- 239000007924 injection Substances 0.000 claims description 53
- -1 nitrogen-containing organic base Chemical class 0.000 claims description 51
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Description
本発明は電荷注入型発光素子に関し、より詳しくは金属ホウ素酸塩あるいは金属ホウ素化合物を用いた有機電荷注入型発光素子に関する。 The present invention relates to a charge injection type light emitting device, and more particularly to an organic charge injection type light emitting device using a metal borate or a metal boron compound.
有機エレクトロルミネッセンス素子(有機EL素子)の開発が盛んである。 Organic electroluminescence elements (organic EL elements) are actively developed.
特許文献1および2では、ドナー(電子供与性)ドーパントとして機能する金属を有する有機層が、陰極に接して設けられている構成が開示されている。そしてこのドナー(電子供与性)ドーパントとして用いられる金属としては、アルカリ金属、アルカリ土類金属、希土類を含む遷移金属等である。これらは金属単体をドープするため化学的安定性が悪く、蒸着室内の微量水分を吸着してしまったり、共蒸着する有機材料を分解してしまう。 Patent Documents 1 and 2 disclose a configuration in which an organic layer having a metal functioning as a donor (electron donating) dopant is provided in contact with a cathode. The metal used as the donor (electron donating) dopant includes alkali metals, alkaline earth metals, transition metals including rare earths, and the like. Since these are doped with a simple metal, they are poor in chemical stability, adsorbing a very small amount of moisture in the deposition chamber, and decomposing the organic material to be co-deposited.
さらに特許文献3では、ドーパントとしてアルカリ金属、アルカリ土類金属、希土類金属の金属酸化物あるいは金属塩を用いているが、ホストとなる有機化合物に比べてこれらの金属酸化物あるいは金属塩の蒸着温度が著しく高くなるため、有機化合物とこれらを共蒸着する際、ホストとなる有機化合物が金属の輻射熱で分解されてしまったり、蒸着室内に付着した有機化合物や、これらの分解物が再度蒸着されてしまうことで、寿命を低下させる原因となるおそれがある。 Further, in Patent Document 3, alkali metal, alkaline earth metal, rare earth metal metal oxide or metal salt is used as a dopant, but the deposition temperature of these metal oxide or metal salt as compared with the organic compound as a host. Therefore, when co-depositing organic compounds and these, the organic compound that becomes the host is decomposed by the radiant heat of the metal, or the organic compounds adhering to the deposition chamber and their decomposition products are again deposited. As a result, there is a risk of reducing the service life.
さらに特許文献4および特許文献5では、電子輸送性の有機化合物と有機金属錯体の混合層が開示されているが、陰極電極が混合層の錯体金属イオンを真空中において金属に還元しうる金属、即ち、Al、Zr、Ti、ScおよびSiに限定されてしまい、Ag、Au、更にはITOやIZO等の透明電極には使用できない。
従って、本発明の目的は化学的安定性が高く、膜の組成の制御が容易であり、かつ共蒸着して用いる場合にもドーパントの蒸着温度が有機化合物と同程度で有機化合物に比較的ダメージを与えにくい電子注入材料を提供し、陰極の電極種を選ばず、極めて高効率で高輝度な光出力を有する有機発光素子、更には極めて耐久性の良い有機発光素子を提供することにある。 Therefore, the object of the present invention is high chemical stability, easy control of the film composition, and even when co-deposited, the dopant deposition temperature is the same as that of the organic compound, and the organic compound is relatively damaged. It is an object to provide an organic light-emitting device having an extremely high efficiency and high-luminance light output, and an extremely durable organic light-emitting device.
本発明の有機発光素子は、陽極及び陰極からなる一対の電極と、前記一対の電極間に挟持された少なくとも一層以上の有機化合物からなる有機発光素子において、前記陰極がAgからなり、前記陰極と前記有機化合物からなる層の間に、金属ホウ素酸塩あるいは金属有機ホウ素化合物を含み、前記陰極に接する電子注入層を有し、前記金属ホウ素酸塩あるいは前記金属有機ホウ素化合物の金属が、アルカリ金属あるいはアルカリ土類金属からなることを特徴とする。また、本発明の有機発光素子は、陽極及び陰極からなる一対の電極と、前記一対の電極間に挟持された少なくとも一層以上の有機化合物からなる有機発光素子において、前記陰極がITOあるいはIZOからなり、前記陰極と前記有機化合物からなる層の間に、金属ホウ素酸塩あるいは金属有機ホウ素化合物を含み、前記陰極に接する電子注入層を有し、前記金属ホウ素酸塩あるいは前記金属有機ホウ素化合物の金属が、アルカリ金属あるいはアルカリ土類金属からなることを特徴とする。また、本発明の有機発光素子は陽極及び陰極からなる一対の電極と、前記一対の電極間に挟持された少なくとも一層以上の有機化合物からなる有機発光素子において、前記陰極がIZOからなり、前記陰極と前記有機化合物からなる層の間に、金属ホウ素酸塩あるいは金属有機ホウ素化合物を含み、前記陰極に接する電子注入層を有し、前記金属ホウ素酸塩あるいは前記金属有機ホウ素化合物の金属が、アルカリ金属あるいはアルカリ土類金属からなることを特徴とする。 The organic light-emitting device of the present invention comprises a pair of electrodes ing an anode and a cathode, the organic light emitting element and the ing from at least one layer of an organic compound is sandwiched between a pair of electrodes, the cathode is made of Ag, the between layers consisting of cathode and the organic compound, see containing a metal borate salt or metal organic boron compound, possess an electronic note sintering bed in contact with the cathode, the metal of the metal borate salt or the metal organic boron compound Is made of an alkali metal or an alkaline earth metal . The organic light-emitting device according to the present invention includes a pair of electrodes composed of an anode and a cathode, and an organic light-emitting device composed of at least one organic compound sandwiched between the pair of electrodes, wherein the cathode is made of ITO or IZO. A metal boronate or a metal organic boron compound between the cathode and the organic compound layer, and an electron injection layer in contact with the cathode, wherein the metal borate or the metal organic boron compound metal Is made of an alkali metal or an alkaline earth metal. The organic light-emitting device of the present invention is a light-emitting device comprising a pair of electrodes comprising an anode and a cathode and at least one organic compound sandwiched between the pair of electrodes, wherein the cathode comprises IZO, And an organic injection layer in contact with the cathode, wherein the metal of the metal borate or the metal organic boron compound is an alkali. It consists of a metal or an alkaline earth metal.
本発明の有機発光素子によれば、電子注入材料として金属ホウ素酸塩或いは金属有機ホウ化物を用いることで、化学的安定性が高く、膜の組成の制御が容易であり、蒸着温度が有機化合物と同程度で有機化合物に比較的ダメージを与えにくい電子注入材料を提供し、極めて高効率で高輝度な光出力と極めて良い耐久性を示す有機発光素子を得ることができた。 According to the organic light emitting device of the present invention, by using a metal borate or a metal organic boride as an electron injecting material, the chemical stability is high, the film composition is easily controlled, and the deposition temperature is an organic compound. As a result, an electron injection material that can hardly damage an organic compound at the same level is provided, and an organic light emitting device that exhibits extremely high efficiency, high luminance light output, and extremely good durability has been obtained.
以下、本発明の有機発光素子の詳細を説明する。 Hereinafter, the details of the organic light emitting device of the present invention will be described.
本発明の有機発光素子は電子注入層に金属ホウ素酸塩あるいは金属有機ホウ素化合物を用いたことを特徴とする。更には、金属ホウ酸塩或いは金属有機ホウ素化物の金属はアルカリ金属或いはアルカリ土類金属からなることを特徴とする。金属ホウ素酸塩あるいは金属有機ホウ素化合物としては特に限定されないが、例えば、四ホウ酸リチウム、四ホウ酸ナトリウム、四ホウ酸カリウム、四ホウ酸ルビジウム、四ホウ酸セシウム、四ホウ酸カルシウム、四ホウ酸ストロンチウム、四ホウ酸バリウム、テトラフルオロホウ酸リチウム、テトラフルオロホウ酸ナトリウム、テトラフルオロホウ酸カリウム、テトラフルオロホウ酸ルビジウム、テトラフルオロホウ酸セシウム、テトラフェニルホウ酸リチウム、テトラフェニルホウ酸ナトリウム、テトラフェニルホウ酸カリウム、テトラフェニルホウ酸ルビジウム、テトラフェニルホウ酸セシウムの水和物あるいは無水和物等が挙げられる。更には、テトラフェニルホウ酸のフェニル基に置換基を付加した化合物、例えばフッ素置換したテトラキス−4−フルオロフェニルホウ酸リチウム、テトラキス−4−フルオロフェニルホウ酸ナトリウム(通称:カリボール)、テトラキス−4−フルオロフェニルホウ酸カリウム、テトラキス−4−フルオロフェニルホウ酸ルビジウム、テトラキス−4−フルオロフェニルホウ酸セシウム、或いは塩素置換したテトラキス−4−クロロフェニルホウ酸リチウム、テトラキス−4−クロロフェニルホウ酸ナトリウム、テトラキス−4−クロロフェニルホウ酸カリウム、テトラキス−4−クロロフェニルホウ酸ルビジウム、テトラキス−4−クロロフェニルホウ酸セシウム、或いはメチル規で置換したテトラキス−p−トリルホウ酸リチウム、テトラキス−p−トリルホウ酸ナトリウム、テトラキス−p−トリルホウ酸カリウム、テトラキス−p−トリルホウ酸ルビジウム、テトラキス−p−トリルホウ酸セシウム、トリフルオロメチル基で置換したテトラキス−4−フルオロメチルフェニルホウ酸リチウム、テトラキス−4−フルオロメチルフェニルホウ酸ナトリウム、テトラキス−4−フルオロメチルフェニルホウ酸カリウム、テトラキス−4−フルオロメチルフェニルホウ酸ルビジウム、テトラキス−4−フルオロメチルフェニルホウ酸セシウム更にはテトラキス−2−チエニルホウ酸リチウム、テトラキス−2−チエニルホウ酸ナトリウム、テトラキス−2−チエニルホウ酸カリウム、テトラキス−2−チエニルホウ酸ルビジウム、テトラキス−2−チエニルホウ酸セシウム、テトラキス−1−イミダゾリルホウ酸リチウム、テトラキス−1−イミダゾリルホウ酸ナトリウム、テトラキス−1−イミダゾリルホウ酸カリウム、テトラキス−1−イミダゾリルホウ酸ルビジウム、テトラキス−1−イミダゾリルホウ酸セシウム等を用いることができる。 The organic light emitting device of the present invention is characterized in that a metal borate or a metal organic boron compound is used for the electron injection layer. Further, the metal of the metal borate or the metal organic borate is characterized by comprising an alkali metal or an alkaline earth metal. Although it does not specifically limit as a metal borate or a metal organoboron compound, For example, lithium tetraborate, sodium tetraborate, potassium tetraborate, rubidium tetraborate, cesium tetraborate, calcium tetraborate, tetraborate Strontium acid, barium tetraborate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, rubidium tetrafluoroborate, cesium tetrafluoroborate, lithium tetraphenylborate, sodium tetraphenylborate, Examples thereof include potassium tetraphenylborate, rubidium tetraphenylborate, and hydrate or anhydrous cesium tetraphenylborate. Further, compounds in which a substituent is added to the phenyl group of tetraphenylboric acid, such as fluorine-substituted lithium tetrakis-4-fluorophenylborate, sodium tetrakis-4-fluorophenylborate (common name: caribol), tetrakis-4 -Potassium fluorophenylborate, rubidium tetrakis-4-fluorophenylborate, cesium tetrakis-4-fluorophenylborate, lithium-substituted tetrakis-4-chlorophenylborate, sodium tetrakis-4-chlorophenylborate, tetrakis Potassium 4-chlorophenylborate, rubidium tetrakis-4-chlorophenylborate, cesium tetrakis-4-chlorophenylborate, or lithium tetrakis-p-tolylborate substituted with methyl Lakis-p-tolylborate sodium, tetrakis-p-tolylborate potassium, tetrakis-p-tolylborate rubidium, tetrakis-p-tolylborate cesium, lithium tetrakis-4-fluoromethylphenylborate substituted with a trifluoromethyl group, Sodium tetrakis-4-fluoromethylphenylborate, potassium tetrakis-4-fluoromethylphenylborate, rubidium tetrakis-4-fluoromethylphenylborate, cesium tetrakis-4-fluoromethylphenylborate, and tetrakis-2-thienylborate Lithium oxide, sodium tetrakis-2-thienylborate, potassium tetrakis-2-thienylborate, rubidium tetrakis-2-thienylborate, cesium tetrakis-2-thienylborate, It is possible to use lithium trakis-1-imidazolylborate, sodium tetrakis-1-imidazolylborate, potassium tetrakis-1-imidazolylborate, rubidium tetrakis-1-imidazolylborate, cesium tetrakis-1-imidazolylborate, and the like. .
四ホウ酸或いはテトラフルオロホウ酸、テトラフェニルホウ酸とその誘導体等とすることで、金属単体、或いは酸化物、ハロゲン化物、窒化物を用いるよりも化学的に安定で、かつ比較的容易に抵抗加熱蒸着ができ、更には四ホウ酸等の蒸着温度が500℃程度、テトラフェニルホウ酸等では300℃〜400℃程度の有機化合物と同等の温度で蒸着できることから、有機化合物との共蒸着においても有機化合物に対して極めてダメージの少ない蒸着が可能となったことから本発明に至った。一般に有機発光素子は水分を嫌うため水和物よりも無水和物の方が好ましいが、たとえ水和物であっても、蒸着時の加熱プロセスの段階で結晶水だけが先に外れるため、無水和物として蒸着を行うことができる。 By using tetraboric acid, tetrafluoroboric acid, tetraphenylboric acid and its derivatives, etc., it is chemically stable and relatively easy to resist than using a single metal, or an oxide, halide, or nitride. In addition, the vapor deposition temperature of tetraboric acid and the like can be deposited at a temperature equivalent to that of an organic compound of about 300 ° C. to 400 ° C. in the case of co-deposition with an organic compound. In addition, the present invention has been achieved because vapor deposition with very little damage to organic compounds has become possible. In general, an organic light-emitting device is preferred to be anhydrous rather than hydrated because it dislikes moisture, but even if it is hydrated, only water of crystallization comes off first in the stage of the heating process during vapor deposition. Vapor deposition can be performed as a Japanese product.
本発明における電子注入層は金属ホウ素酸塩あるいは金属有機ホウ素化合物を単層で、あるいは、これらの材料と電子輸送性の有機材料との混合層のいずれかで選択して使用することが出来る。本発明では単層でもよいことを含めた意味で電子注入輸送層は金属ホウ素酸塩あるいは金属有機ホウ素化合物を含むということができる。 The electron injection layer in the present invention can be selected and used as a single layer of a metal borate or a metal organic boron compound or a mixed layer of these materials and an electron transporting organic material. In the present invention, it can be said that the electron injecting and transporting layer contains a metal borate or a metal organic boron compound in the sense that it may be a single layer.
また、陰極とこの有機化合物層の間に別な層を設けてもよい。この別な層とは有機層あるいは無機層あるいは、有機・無機の混合層でもよい。更に具体的には、LiF層であってもよい。なお、そのような別の層を設けることで、電子注入が更に改善される。そして、この別な層が設けられていても陰極とこの有機化合物層は、実質電気的に接していると言える。 Further, another layer may be provided between the cathode and the organic compound layer. This other layer may be an organic layer, an inorganic layer, or an organic / inorganic mixed layer. More specifically, a LiF layer may be used. In addition, electron injection is further improved by providing such another layer. And even if this other layer is provided, it can be said that the cathode and the organic compound layer are in substantial electrical contact.
本発明における電子注入層として金属ホウ素酸塩あるいは金属有機ホウ素化合物を単層で用いる場合の厚みは特に限定されないが、1〜1000Åが好ましい。1Å未満では十分な電子注入性が得られず、また、1000Åを超えるとキャリアの移動がなくなるため好ましくない。 Although the thickness in the case of using a metal borate or a metal organic boron compound as a single layer as the electron injection layer in the present invention is not particularly limited, it is preferably 1 to 1000 mm. If it is less than 1 mm, sufficient electron injectability cannot be obtained, and if it exceeds 1000 mm, carrier movement is lost.
混合層で用いる場合にも、厚みは特に限定されないが1〜3000Åが好ましい。1Å未満では電極界面近傍に存在する注入金属分子の量が少ないので注入性が向上せず、また3000Åを超えると有機膜全体の膜厚が厚くなり過ぎるため、駆動電圧の上昇を招くので好ましくない。 Even when used in the mixed layer, the thickness is not particularly limited, but is preferably 1 to 3000 mm. If it is less than 1 mm, the amount of injected metal molecules present in the vicinity of the electrode interface is small, so that the injectability is not improved, and if it exceeds 3000 mm, the entire organic film becomes too thick, leading to an increase in driving voltage. .
混合層の金属ホウ酸塩のドーピング量は特に限定されないが、1〜99重量%であることが望ましい。特に1重量%未満では、ドーパントの濃度が低すぎるのでドーピング効果が小さい。 The doping amount of the metal borate in the mixed layer is not particularly limited, but is desirably 1 to 99% by weight. In particular, if it is less than 1% by weight, the doping effect is small because the concentration of the dopant is too low.
上記電子注入層の成膜方法はいかなる薄膜形成法であってもよく、例えば、蒸着法やスパッタ法が使用できる。 The electron injecting layer may be formed by any thin film forming method, for example, vapor deposition or sputtering.
混合層に使用できる有機化合物としては、発光層、電子輸送層として使用可能な有機化合物であれば特に限定はないが、例えば、ナフタレン、アントラセン、テトラセン、ピレン、クリセン、コロネン、ナフタセン、フェナントレンなどの縮合多環炭化水素化合物およびそれらの誘導体、アクリジン、キノリン、キノキサリンなどの縮合複素環化合物およびそれらの誘導体、あるいは、ペリレン、フタロペリレン、ナフタロペリレン、ペリノン、フタロペリノン、ナフタロペリノン、オキサジアゾール、フルオレン、フルオロセイン、ジフェニルブタジエン、テトラフェニルブタジエン、ビスベンゾキサゾリン、ビススチリル、ピラジン、シクロペンタジエンオキシン、アミノキノリン、イミン、ジフェニルエチレン、ビニルアントラセン、ジアミノカルバゾール、ピラン、チオピラン、ポリメチン、メロシアニン、キナクリドン、ルブレンとそれらの誘導体、含窒素有機塩基の例としてはフェナントロリン、バソフェナントロリン、フェナントリジン、ピリジン、ビピリジン、ターピリジンおよびそれらの誘導体、トリス(8―キノリノラト)アルミニウムのような金属錯体等を挙げることができる。 The organic compound that can be used in the mixed layer is not particularly limited as long as it is an organic compound that can be used as a light-emitting layer and an electron transport layer.For example, naphthalene, anthracene, tetracene, pyrene, chrysene, coronene, naphthacene, phenanthrene, and the like. Fused polycyclic hydrocarbon compounds and derivatives thereof, condensed heterocyclic compounds such as acridine, quinoline, quinoxaline and derivatives thereof, or perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, oxadiazole, fluorene, fluorescein, Diphenylbutadiene, tetraphenylbutadiene, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadienoxin, aminoquinoline, imine, diphenylethylene, vinylanthracene, Examples of aminocarbazole, pyran, thiopyran, polymethine, merocyanine, quinacridone, rubrene and their derivatives, and nitrogen-containing organic bases include phenanthroline, bathophenanthroline, phenanthridine, pyridine, bipyridine, terpyridine and their derivatives, tris (8- (Quinolinolato) metal complexes such as aluminum.
特に含窒素有機塩基を含む有機材料と本発明の金属ホウ素酸塩あるいは金属ホウ素化合物による混合層の場合には極めて良い電子注入効果が得られる。 In particular, in the case of a mixed layer of an organic material containing a nitrogen-containing organic base and the metal borate or metal boron compound of the present invention, a very good electron injection effect can be obtained.
このような有機発光素子は、ディスプレイの画素として利用することができる。ディスプレイの有効表示領域の画素は例えば赤青緑のような色毎にそれぞれ画素を有している。そして各色の画素に対応する有機発光素子に本発明の発光素子を適用することができる。もちろん単色表示のディスプレイの画素に本発明の有機発光素子を用いてもよい。 Such an organic light emitting device can be used as a pixel of a display. The pixels in the effective display area of the display have pixels for each color such as red, blue, and green. The light-emitting element of the present invention can be applied to organic light-emitting elements corresponding to pixels of each color. Of course, the organic light-emitting element of the present invention may be used for a pixel of a monochrome display.
また複数の有機発光素子を有する有機発光素子アレイに本発明の有機発光素子を用いてもよい。複数の有機発光素子を発光させるにはそれぞれの有機発光素子にスイッチング素子を配置することが好ましく、その場合それぞれの有機発光素子ごとに発光、非発光をコントロールすることができる。スイッチング素子は薄膜トランジスタであることが好ましい。このような薄膜トランジスタを有する有機発光素子を2次元状に配置させることで2次元画像表示が可能となる。また薄膜トランジスタが配置されている側の基板から光をとりだす構成もよいが、反対側から光を取り出す構成の有機発光素子にも好ましく適用できる。その場合透明電極を基板と反対側に配置することが好ましく、透明電極として陰極を用いてもよい。 Moreover, you may use the organic light emitting element of this invention for the organic light emitting element array which has a some organic light emitting element. In order to cause a plurality of organic light emitting elements to emit light, it is preferable to arrange a switching element in each organic light emitting element. In this case, light emission and non-light emission can be controlled for each organic light emitting element. The switching element is preferably a thin film transistor. Two-dimensional image display is possible by arranging such organic light-emitting elements having thin film transistors in a two-dimensional manner. Moreover, although the structure which takes out light from the board | substrate of the side in which the thin-film transistor is arrange | positioned is good, it can apply preferably also to the organic light emitting element of the structure which takes out light from the other side. In that case, it is preferable to dispose the transparent electrode on the opposite side of the substrate, and a cathode may be used as the transparent electrode.
以下、本実施形態について、図面に沿って詳細に説明する。 Hereinafter, the present embodiment will be described in detail with reference to the drawings.
図1〜図6に本発明の有機発光素子の構成例を示す。 1 to 6 show configuration examples of the organic light emitting device of the present invention.
図1は、本発明の有機発光素子の一例を示す断面図である。図1は、基板1上に、陽極2、発光層3、電子注入層4及び陰極5を順次設けた構成のものである。この場合は、ここで使用する発光材料は、それ自身でホール輸送能、エレクトロン輸送能及び発光性の性能を単一で有している場合や、それぞれの特性を有する化合物を混ぜて使う場合に有用である。 FIG. 1 is a cross-sectional view showing an example of the organic light emitting device of the present invention. FIG. 1 shows a structure in which an anode 2, a light emitting layer 3, an electron injection layer 4 and a cathode 5 are sequentially provided on a substrate 1. In this case, the luminescent material used here has a single hole transport ability, electron transport ability and luminescent performance by itself, or a mixture of compounds having the respective characteristics. Useful.
図2は、本発明の有機発光素子における他の例を示す断面図である。図2は、基板1上に、陽極2、ホール輸送層6、電子輸送層7、電子注入層4及び陰極5を順次設けた構成のものである。この場合は、発光物質はホール輸送性かあるいは電子輸送性のいずれか、あるいは両方の機能を有している材料をそれぞれの層に用い、発光性の無い単なるホール輸送物質あるいは電子輸送物質と組み合わせて用いる場合に有用である。また、この場合、発光層3は、ホール輸送層6あるいは電子輸送層7のいずれかから成る。 FIG. 2 is a cross-sectional view showing another example of the organic light emitting device of the present invention. FIG. 2 shows a configuration in which an anode 2, a hole transport layer 6, an electron transport layer 7, an electron injection layer 4 and a cathode 5 are sequentially provided on a substrate 1. In this case, the light emitting material is either a hole transporting property or an electron transporting property, or a material having both functions is used for each layer, and it is combined with a simple hole transporting material or an electron transporting material having no light emitting property. This is useful when used. In this case, the light emitting layer 3 is composed of either the hole transport layer 6 or the electron transport layer 7.
図3は、本発明の有機発光素子における他の例を示す断面図である。図3は、基板1上に、陽極2、ホール輸送層6、発光層3、電子輸送層7、電子注入層4及び陰極5を順次設けた構成のものである。これは、キャリヤ輸送と発光の機能を分離したものであり、ホール輸送性、電子輸送性、発光性の各特性を有した化合物と適時組み合わせて用いられ、極めて材料選択の自由度が増すとともに、発光波長を異にする種々の化合物が使用できるため、発光色相の多様化が可能になる。さらに、中央の発光層3に各キャリヤあるいは励起子を有効に閉じこめて、発光効率の向上を図ることも可能になる。 FIG. 3 is a cross-sectional view showing another example of the organic light emitting device of the present invention. FIG. 3 shows a structure in which an anode 2, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 4 and a cathode 5 are sequentially provided on a substrate 1. This is a function that separates the functions of carrier transport and light emission, and is used in combination with compounds having hole transport properties, electron transport properties, and light emission properties in a timely manner, and the degree of freedom of material selection is greatly increased. Since various compounds having different emission wavelengths can be used, the emission hue can be diversified. Further, it is possible to effectively confine each carrier or exciton in the central light emitting layer 3 to improve the light emission efficiency.
図4は、本発明の有機発光素子における他の例を示す断面図である。図4は、図3に対して、ホール注入層8を陽極2側に挿入した構成であり、陽極2とホール輸送層6の密着性改善あるいはホールの注入性改善に効果があり、低電圧化に効果的である。 FIG. 4 is a cross-sectional view showing another example of the organic light emitting device of the present invention. FIG. 4 shows a structure in which a hole injection layer 8 is inserted on the anode 2 side with respect to FIG. 3, and is effective in improving the adhesion between the anode 2 and the hole transport layer 6 or improving the hole injection property. It is effective.
図5は、本発明の有機発光素子における他の例を示す断面図である。図5は、図3に対してホールあるいは励起子(エキシトン)を陰極5側に抜けることを阻害する層(ホールブロッキング層9)を、発光層3、電子輸送層7間に挿入した構成である。イオン化ポテンシャルの非常に高い化合物をホールブロッキング層9として用いる事により、発光効率の向上に効果的な構成である。 FIG. 5 is a cross-sectional view showing another example of the organic light emitting device of the present invention. FIG. 5 shows a structure in which a layer (hole blocking layer 9) that prevents holes or excitons (excitons) from passing to the cathode 5 side is inserted between the light emitting layer 3 and the electron transport layer 7. . By using a compound having a very high ionization potential as the hole blocking layer 9, the structure is effective in improving the light emission efficiency.
図6は図4と図5の構成を組み合わせた構成である。 FIG. 6 is a combination of the configurations of FIG. 4 and FIG.
ただし、図1〜図6はあくまで、ごく基本的な素子構成であり、本発明の化合物を用いた有機発光素子の構成はこれらに限定されるものではない。例えば、電極と有機層界面に絶縁性層を設ける、接着層あるいは干渉層を設ける、ホール輸送層がイオン化ポテンシャルの異なる2層から構成される、など多様な層構成をとることができる。 However, FIG. 1 to FIG. 6 are very basic device configurations, and the configuration of the organic light emitting device using the compound of the present invention is not limited thereto. For example, various layer configurations such as providing an insulating layer at the interface between the electrode and the organic layer, providing an adhesive layer or an interference layer, and the hole transport layer including two layers having different ionization potentials can be employed.
本発明は上記の多様な構成の発光層または、発光領域に関するものであり、いずれの構成でも実施可能である。その他の構成成分としては、これまで知られている低分子系のホール輸送性化合物、発光材料、電子輸送性化合物、高分子系材料などを必要に応じて用いることができる。 The present invention relates to a light emitting layer or a light emitting region having various configurations described above, and can be implemented with any configuration. As other components, known low molecular weight hole transport compounds, light emitting materials, electron transport compounds, polymer materials, and the like can be used as necessary.
陰極材料としては、一般に仕事関数の小さなものがよく、リチウム、ナトリウム、カリウム、カルシウム、マグネシウム、アルミニウム、インジウム等の金属単体あるいは複数の合金として用いることができる。また、陰極は一層構成でもよく、多層構成をとることもできる。特開2000−182774号公報およびUS6396209号公報では、陰極材料として還元性のある金属、すなわち、アルミニウム、ジルコニウム、チタン、イットリウム、スカンジウム、シリコン等を用い、電子注入層の構成材料である金属イオンを真空中で金属に還元、遊離させ、さらにこの遊離金属で有機化合物を還元することにより電子注入障壁を小さくし、駆動電圧を低下させると記載されているが、本発明の金属ホウ素酸塩あるいは金属ホウ素化合物を電子注入層に用いた場合には、還元性のない金属を陰極電極として用いても電子注入性を向上させることができる。さらに陰極に用いる材料の仕事関数に制限されないため、広範な材料の中から陰極電極の材料を選択することができ、金、銀、白金、ニッケル、パラジウム、コバルト、セレン、バナジウム、鉛、錫、クロム等比較的仕事関数の大きな金属単体やこれらの合金の他、酸化錫インジウム(ITO),酸化亜鉛インジウム(IZO)、酸化亜鉛アルミニウム(AZO、IXO等の金属酸化物を用いた可視光に対して透明な電極の利用も可能である。透明陰極電極の可視光領域、即ち400nmから700nmの波長領域での透過率は70%以上であることが望ましい。 The cathode material generally has a small work function, and can be used as a single metal or a plurality of alloys such as lithium, sodium, potassium, calcium, magnesium, aluminum, and indium. Further, the cathode may have a single layer structure or a multilayer structure. In Japanese Unexamined Patent Publication No. 2000-182774 and US Pat. No. 6,396,209, a metal having a reducing property as a cathode material, that is, aluminum, zirconium, titanium, yttrium, scandium, silicon, or the like is used, and metal ions that are constituent materials of an electron injection layer are used. Although it is described that the electron injection barrier is reduced by reducing and liberating the metal in vacuum and further reducing the organic compound with this free metal, the driving voltage is reduced. When a boron compound is used for the electron injection layer, the electron injection property can be improved even when a non-reducing metal is used as the cathode electrode. Furthermore, since the work function of the material used for the cathode is not limited, the cathode electrode material can be selected from a wide range of materials, such as gold, silver, platinum, nickel, palladium, cobalt, selenium, vanadium, lead, tin, In addition to chromium and other metals having a relatively high work function and alloys thereof, in addition to visible light using metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), and zinc oxide aluminum (AZO, IXO) The transparent cathode electrode preferably has a transmittance of 70% or more in the visible light region, that is, in the wavelength region of 400 to 700 nm.
一方、陽極材料としては、仕事関数がなるべく大きなものがよく、例えば、金、銀、白金、ニッケル、パラジウム、コバルト、セレン、バナジウム、鉛、錫、クロム等の金属単体あるいはこれらの合金、酸化錫、酸化亜鉛、酸化錫インジウム(ITO),酸化亜鉛インジウム(IZO)、酸化亜鉛アルミニウム(AZO)、IXO等の金属酸化物が使用できる。また、ポリアニリン、ポリピロール、ポリチオフェン、ポリフェニレンスルフィド等の導電性ポリマーも使用できる。これらの電極物質は単独で用いてもよく、複数併用することもできる。 On the other hand, the anode material preferably has a work function as large as possible, for example, gold, silver, platinum, nickel, palladium, cobalt, selenium, vanadium, lead, tin, chromium, or other simple metals or alloys thereof, tin oxide Metal oxides such as zinc oxide, indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), and IXO can be used. In addition, conductive polymers such as polyaniline, polypyrrole, polythiophene, and polyphenylene sulfide can also be used. These electrode materials may be used alone or in combination.
陰極電極が透明であり、陰極側から光を取り出す場合には、陽極は可視光領域で反射性の高い電極であることが望ましく、クロム(Cr)電極あるいは銀(Ag)電極又はこれらのうちいずれかを含む合金からなる電極であることが好ましく、反射率は400nmから700nmの波長領域で70%以上であることが望ましい。特にAg−Ru−Au合金(通称ARA)や、Ag―Ru−Cu合金のように反射率が85%以上のものは光の取り出し効率が良く特に好ましい。 When the cathode electrode is transparent and light is extracted from the cathode side, the anode is preferably an electrode having high reflectivity in the visible light region. Either a chromium (Cr) electrode or a silver (Ag) electrode or any of these It is preferable that the electrode is made of an alloy containing the above, and the reflectance is desirably 70% or more in a wavelength region of 400 nm to 700 nm. In particular, an Ag—Ru—Au alloy (commonly known as ARA) or an Ag—Ru—Cu alloy having a reflectance of 85% or more is particularly preferable because of good light extraction efficiency.
本発明で用いる基板としては、特に限定するものではないが、金属製基板、セラミックス製基板等の不透明性基板、ガラス、石英、プラスチックシート等の透明性基板が用いられる。また、基板にカラーフィルター膜、蛍光色変換フィルター膜、誘電体反射膜などを用いて発色光をコントロールする事も可能である。 Although it does not specifically limit as a board | substrate used by this invention, Transparent substrates, such as opaque board | substrates, such as a metal board | substrate and a ceramic board | substrate, glass, quartz, a plastic sheet, are used. It is also possible to control the color light by using a color filter film, a fluorescent color conversion filter film, a dielectric reflection film, or the like on the substrate.
なお、作成した素子に対して、酸素や水分等との接触を防止する目的で保護層あるいは封止層を設けることもできる。保護層としては、ダイヤモンド薄膜、金属酸化物、金属窒化物等の無機材料膜、フッ素樹脂、ポリパラキシレン、ポリエチレン、シリコーン樹脂、ポリスチレン樹脂等の高分子膜、さらには、光硬化性樹脂等が挙げられる。また、ガラス、気体不透過性フィルム、金属などをカバーし、適当な封止樹脂により素子自体をパッケージングすることもできる。 Note that a protective layer or a sealing layer can be provided on the prepared element for the purpose of preventing contact with oxygen or moisture. Examples of protective layers include diamond thin films, inorganic material films such as metal oxides and metal nitrides, polymer films such as fluororesins, polyparaxylene, polyethylene, silicone resins, and polystyrene resins, and photocurable resins. Can be mentioned. Further, it is possible to cover glass, a gas impermeable film, a metal, etc., and to package the element itself with an appropriate sealing resin.
(実施例)
以下、実施例により本発明をさらに具体的に説明していくが、本発明はこれらに限定されるものではない。
(Example)
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
(参考例1)
ガラス基板上に陽極として酸化錫インジウム(ITO)をスパッタ法にて1200Åの膜厚で成膜したものを透明導電性支持基板として用いた。これをアセトン、イソプロピルアルコール(IPA)で順次超音波洗浄し、IPAで煮沸洗浄、乾燥をした。さらに、UV/オゾン洗浄した。
( Reference Example 1)
An indium tin oxide (ITO) film formed by sputtering on a glass substrate to a thickness of 1200 mm was used as a transparent conductive support substrate. This was ultrasonically washed successively with acetone and isopropyl alcohol (IPA), boiled and washed with IPA, and dried. Further, UV / ozone cleaning was performed.
この基板上に、まず、ホール輸送材料として、α−NPD(下記式[1])を400Å、次に発光層として、トリス(8―キノリノラト)アルミニウム(以下Alq3と記載する(下記式[2]))にクマリン6(下記式[3])を1%ドープした化合物200Åを順次真空蒸着した。さらに、電子輸送層として式[4]に示されるバソフェナントロリン系化合物を400Å真空蒸着した。 On this substrate, first, α-NPD (the following formula [1]) is 400Å as a hole transport material, and then tris (8-quinolinolato) aluminum (hereinafter referred to as Alq3) is used as a light emitting layer (the following formula [2] )) Was sequentially vacuum-deposited with 200% of a compound doped with 1% of coumarin 6 (the following formula [3]). Further, a bathophenanthroline-based compound represented by the formula [4] was vacuum-deposited for 400 mm as an electron transport layer.
次に、電子注入層として四ホウ酸ナトリウムを真空蒸着法で5Å成膜した後、真空蒸着法でAlを1500Å形成し、有機EL素子を作成した。 Next, 5 μm of sodium tetraborate was formed as an electron injection layer by vacuum deposition, and then 1500 μm of Al was formed by vacuum deposition to produce an organic EL device.
蒸着時の真空度は2×10−4Paであり、有機層の成膜速度は1Å/s、陰極は10Å/sであった。 The degree of vacuum at the time of vapor deposition was 2 × 10 −4 Pa, the film formation rate of the organic layer was 1 、 / s, and the cathode was 10 Å / s.
四ホウ酸ナトリウムは蒸着も容易で安定した薄膜が得られた。 Sodium tetraborate was easily deposited and a stable thin film was obtained.
この様にして得られた素子のITO電極を正極、Al電極を負極にして、20mA/cm2で駆動したところ、4.4Vの電圧を示し、約1750cd/m2の緑色発光が得られ、発光効率は6.1lm/W、外部量子効率は2.5%であった。 When the ITO electrode of the device thus obtained was used as the positive electrode and the Al electrode as the negative electrode and was driven at 20 mA / cm 2, it showed a voltage of 4.4 V and green light emission of about 1750 cd / m 2 was obtained. The luminous efficiency was 6.1 lm / W, and the external quantum efficiency was 2.5%.
さらに、素子を電流密度100mA/cm2の定電流で駆動し、初期輝度の減衰変化と経過時間の関係を調べたところ、初期輝度が半減するまでに要した時間は約600時間であった。 Further, when the device was driven at a constant current of 100 mA / cm 2 and a relationship between the attenuation change of the initial luminance and the elapsed time was examined, the time required for the initial luminance to be halved was about 600 hours.
(比較例1)
電子注入層なしで、Al電極を直接化合物[4]層に積層した以外は、参考例1と同じ構成の素子を作成した。
(Comparative Example 1)
A device having the same configuration as that of Reference Example 1 was prepared except that an Al electrode was directly laminated on the compound [4] layer without an electron injection layer.
この素子のITO電極を正極、Al電極を負極にして、20mA/cm2で駆動したところ、13.2Vの電圧を示し、約270cd/m2の緑色発光が得られ、発光効率は0.3lm/W、外部量子効率は0.4%であった。 When this element was driven at 20 mA / cm 2 with the ITO electrode as the positive electrode and the Al electrode as the negative electrode, it showed a voltage of 13.2 V, green light emission of about 270 cd / m 2 was obtained, and the luminous efficiency was 0.3 lm. / W, the external quantum efficiency was 0.4%.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は1時間未満であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was less than 1 hour.
以上、参考例1と比較例1を比較すると、本発明による金属ホウ酸塩を用いた実施例1では電子注入層のない比較例1よりも低電圧で駆動でき、発光効率も高く、電子注入層としての効果は非常に大きかった。 As described above, when Reference Example 1 and Comparative Example 1 are compared, Example 1 using the metal borate according to the present invention can be driven at a lower voltage than Comparative Example 1 without the electron injection layer, has higher luminous efficiency, and has a higher electron efficiency. The effect as a layer was very large.
さらに、素子の連続駆動による劣化は四ホウ酸ナトリウムにより著しく改善されていた。 Furthermore, deterioration due to continuous driving of the element was remarkably improved by sodium tetraborate.
(参考例2)
参考例1で用いた洗浄済みのITO付き透明導電性支持基板上に、ホール輸送材料として、式[1]に示されるα−NPDを400Å、次に発光層として式[2]に示されるAlq3に式[3]に示されるクマリン6を1%ドープした化合物を200Å、さらに、電子輸送層として式[4]に示されるバソフェナントロリン化合物を200Å真空蒸着した。次に電子注入層として、式[4]のバソフェナントロリン化合物と四ホウ酸カリウム無水和物をモル比がほぼ1:2になるように共蒸着し150Åの厚みに形成した。次いで真空蒸着法でAlを1500Å形成し、有機EL素子を作成した。
( Reference Example 2)
On the transparent conductive support substrate with ITO used in Reference Example 1, 400 μg of α-NPD represented by the formula [1] is used as the hole transport material, and then Alq3 represented by the formula [2] is used as the light emitting layer. In addition, 200% of a compound doped with 1% of coumarin 6 represented by the formula [3] was further vacuum-deposited with 200% of a bathophenanthroline compound represented by the formula [4] as an electron transport layer. Next, as an electron injection layer, a bathophenanthroline compound of the formula [4] and potassium tetraborate anhydrate were co-deposited so as to have a molar ratio of approximately 1: 2, and a thickness of 150 mm was formed. Subsequently, 1500 liters of Al was formed by a vacuum evaporation method, and an organic EL element was produced.
得られた素子を参考例1と同様に20mA/cm2で駆動したところ、4.2Vの電圧を示し、約1780cd/m2の緑色発光が得られ、発光効率は6.6lm/W、外部量子効率は2.6%であった。 When the obtained device was driven at 20 mA / cm 2 in the same manner as in Reference Example 1, a voltage of 4.2 V was obtained, green light emission of about 1780 cd / m 2 was obtained, luminous efficiency was 6.6 lm / W, external The quantum efficiency was 2.6%.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約550時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 550 hours.
本実施例では四ホウ酸カリウムと電子輸送性の有機化合物を共蒸着して電子注入層としたが、注入層なしの比較例1と比べて大幅に電子注入性が向上し、素子劣化も大幅に改善されていた。 In this example, potassium tetraborate and an electron-transporting organic compound were co-evaporated to form an electron injection layer, but the electron injection property was significantly improved and device deterioration was greatly improved as compared with Comparative Example 1 without the injection layer. It was improved.
(実施例1)
参考例2と同様の構成で、陰極電極をAlの代わりにAgを用いた。得られた素子を20mA/cm2で駆動したところ、4.4Vの電圧を示し、約1720cd/m2の緑色発光が得られ、発光効率は6.1lm/W、外部量子効率は2.5%であり、Al電極並みの特性が得られた。
(Example 1 )
In the same configuration as in Reference Example 2, Ag was used for the cathode electrode instead of Al . When the obtained device was driven at 20 mA / cm 2 , a voltage of 4.4 V was exhibited, green light emission of about 1720 cd / m 2 was obtained, the light emission efficiency was 6.1 lm / W, and the external quantum efficiency was 2.5. %, And the same characteristics as the Al electrode were obtained.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約500時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 500 hours.
本発明の金属ホウ酸塩を用い、電子注入材料と共蒸着した場合には、陰極電極に還元性のない金属を用いても、電子の注入性が向上するため、陰極材料として広範囲の材料を選択することができる。 When the metal borate of the present invention is used and co-evaporated with an electron injection material, even if a non-reducing metal is used for the cathode electrode, the electron injection property is improved. You can choose.
(参考例3)
参考例1で用いた素子の電子注入層を四ホウ酸リチウムの替わりに、テトラフェニルホウ酸ルビジウムを20Å蒸着した後、Alを1500Å形成し、有機EL素子を作成した。
( Reference Example 3 )
Instead of lithium tetraborate, 20 g of rubidium tetraphenylborate was deposited on the electron injection layer of the device used in Reference Example 1, and then 1500 g of Al was formed to produce an organic EL device.
テトラフェニルホウ酸ルビジウムは蒸着も容易で安定した薄膜が得られた。 The rubidium tetraphenylborate was easy to deposit and a stable thin film was obtained.
得られた素子を20mA/cm2で駆動したところ、4.0Vの電圧を示し、約1600cd/m2の緑色発光が得られ、発光効率は6.3lm/W、外部量子効率は2.3%であった。 When the obtained device was driven at 20 mA / cm 2 , a voltage of 4.0 V was exhibited, green light emission of about 1600 cd / m 2 was obtained, the light emission efficiency was 6.3 lm / W, and the external quantum efficiency was 2.3. %Met.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約550時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 550 hours.
(実施例2)
参考例3と同様の構成で、Al電極の替わりに、Ag電極を真空蒸着法で設けた。得られた素子を20mA/cm2で駆動したところ、5.7Vの電圧を示し、約1620cd/m2の緑色発光が得られ、発光効率は4.5lm/W、外部量子効率は2.3%であった。
(Example 2 )
In the same configuration as in Reference Example 3 , an Ag electrode was provided by a vacuum deposition method instead of the Al electrode. When the obtained device was driven at 20 mA / cm 2, it showed a voltage of 5.7 V, green light emission of about 1620 cd / m 2 was obtained, the light emission efficiency was 4.5 lm / W, and the external quantum efficiency was 2.3. %Met.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約500時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 500 hours.
(比較例2)
電子注入層としてフッ化リチウム(LiF)を5Å、更に陰極電極としてAlの代わりにAgを用いた以外は参考例1と同じ構成の素子を作成した。20mA/cm2で駆動したところ、8.5Vを示し、約540cd/m2の緑色発光が得られ、発光効率は1.0lm/W、外部量子効率は0.8%であった。
(Comparative Example 2)
A device having the same configuration as that of Reference Example 1 was prepared except that lithium fluoride (LiF) was used as an electron injection layer and 5 mm was used instead of Al as a cathode electrode. When driven at 20 mA / cm 2, it showed 8.5 V, green light emission of about 540 cd / m 2 was obtained, the light emission efficiency was 1.0 lm / W, and the external quantum efficiency was 0.8%.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は10時間未満であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was less than 10 hours.
本比較例では、フッ化リチウムのような電子注入層を設けても陰極電極に還元性のない金属を用いた場合には電子の注入性が向上しないことを示している。それに対し、本実施例2では、参考例3と比較しても大きな電子注入効果の低下もなく、電子注入層のない比較例1と比べても明らかに電子注入効果があった。 This comparative example shows that even when an electron injection layer such as lithium fluoride is provided, when a non-reducible metal is used for the cathode electrode, the electron injection property is not improved. On the other hand, in Example 2 , there was no significant decrease in the electron injection effect compared with Reference Example 3, and there was clearly an electron injection effect compared with Comparative Example 1 without the electron injection layer.
(参考例4)
参考例2と同様の構成で、電子注入層として式[4]に示されるバソフェナントロリンとテトラフェニルホウ酸ナトリウムをモル比がほぼ2:1になるように共蒸着した。次いで真空蒸着法でAlを1500Å形成し、素子を作成した。
( Reference Example 4 )
In the same configuration as in Reference Example 2, as the electron injection layer, bathophenanthroline represented by Formula [4] and sodium tetraphenylborate were co-deposited so that the molar ratio was approximately 2: 1. Subsequently, 1500 liters of Al was formed by a vacuum deposition method, and an element was produced.
テトラフェニルホウ酸ナトリウムは蒸着も容易で、安定した共蒸着薄膜が得られた。 Sodium tetraphenylborate was easily deposited, and a stable co-deposited thin film was obtained.
この様にして得られた素子を参考例1と同様に20mA/cm2で駆動したところ、3.9Vの電圧を示し、約1810cd/m2の緑色発光が得られ、発光効率は7.3lm/W、外部量子効率は2.6%であった。 When the device thus obtained was driven at 20 mA / cm 2 in the same manner as in Reference Example 1, a voltage of 3.9 V was obtained, green light emission of about 1810 cd / m 2 was obtained, and the light emission efficiency was 7.3 lm. / W, the external quantum efficiency was 2.6%.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約600時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 600 hours.
電子注入層としてテトラフェニルホウ酸ナトリウムを添加したことで、電子注入層のない比較例2よりも発光特性が著しく改善されていた。 By adding sodium tetraphenylborate as the electron injection layer, the light emission characteristics were remarkably improved as compared with Comparative Example 2 without the electron injection layer.
(実施例3)
参考例4と同様の構成で、陰極電極をAlの代わりにAgを用いた。得られた素子を20mA/cm2で駆動したところ、4.1Vの電圧を示し、約1600cd/m2の緑色発光が得られ、発光効率は6.1lm/W、外部量子効率は2.3%であり、Al電極並みの特性が得られた。
(Example 3 )
In the same configuration as in Reference Example 4 , Ag was used for the cathode electrode instead of Al . When the obtained device was driven at 20 mA / cm 2 , a voltage of 4.1 V was exhibited, green light emission of about 1600 cd / m 2 was obtained, the light emission efficiency was 6.1 lm / W, and the external quantum efficiency was 2.3. %, And the same characteristics as the Al electrode were obtained.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は550時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was 550 hours.
(参考例5)
参考例4と同様の構成で、陰極電極をAlの代わりにAuを用いた。得られた素子を20mA/cm2で駆動したところ、4.1Vの電圧を示し、約1350cd/m2の緑色発光が得られ、発光効率は5.2lm/W、外部量子効率は2.0%であった。
( Reference Example 5 )
In the same configuration as in Reference Example 4 , Au was used for the cathode electrode instead of Al . When the obtained device was driven at 20 mA / cm 2 , a voltage of 4.1 V was exhibited, green light emission of about 1350 cd / m 2 was obtained, the light emission efficiency was 5.2 lm / W, and the external quantum efficiency was 2.0. %Met.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約550時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 550 hours.
Au電極はAlやAg電極と比較して陰極での光の反射率が小さいため素子の輝度・発光効率および外部量子効率の点でAl或いはAg電極を用いた素子よりも若干劣るが、電圧−電流特性は3者でほぼ同等であった。 The Au electrode is slightly inferior to the element using the Al or Ag electrode in terms of the brightness / light emission efficiency of the element and the external quantum efficiency because the reflectance of light at the cathode is smaller than that of the Al or Ag electrode. The current characteristics were almost the same among the three.
このように陰極電極に還元性のない金属を用いても、電子の注入性が向上し、更に陰極材料によらず優れた電子注入性を示していた。 Thus, even when a non-reducible metal was used for the cathode electrode, the electron injection property was improved, and excellent electron injection property was exhibited regardless of the cathode material.
(実施例4)
本実施例は、陽極に、反射電極として機能するクロム(Cr)、陰極に、透明な発光取り出し電極として機能するインジウム錫酸化物(ITO)を用いた発光素子、すなわちトップエミッション型素子への適用例を示す。
(Example 4 )
This embodiment is applied to a light emitting element using chromium (Cr) functioning as a reflective electrode for the anode and indium tin oxide (ITO) functioning as a transparent light extraction electrode for the cathode, that is, a top emission type element. An example is shown.
基板上にクロム(Cr)をDCスパッタ法にて2000Åの膜厚で成膜し、陽極電極を得た。スパッタガスとしてアルゴンガスを用い、圧力を0.2Pa、DC出力を300Wとした。その後、前記基板をUV/オゾン洗浄した後、蒸着機に移した。続いて、陽極電極であるクロム(Cr)の上にまず正孔注入材料として銅フタロシアニン(下記式[5])を100Å蒸着した。以下、実施例1と同様な条件にて、輸送層として式[1]に示したα―NPDを500Åの膜厚で成膜し、その上に発光層として、式[3]に示したクマリン6(1.0wt%)と式[2]に示したAlq3の共蒸着膜を300Åの膜厚で成膜した。次に電子輸送層として式[4]に示したバソフェナントロリンを200Å成膜し、更にバソフェナントロリンとテトラフェニルホウ酸カリウムを膜厚比9:1の割合で混合されるよう、各々の蒸着速度を調整して300Åの厚さに電子注入材料を成膜した。 Chromium (Cr) was deposited on the substrate by DC sputtering to a thickness of 2000 mm to obtain an anode electrode. Argon gas was used as the sputtering gas, the pressure was 0.2 Pa, and the DC output was 300 W. Thereafter, the substrate was UV / ozone cleaned and then transferred to a vapor deposition machine. Subsequently, copper phthalocyanine (the following formula [5]) was vapor-deposited as a hole injecting material on chromium (Cr) serving as the anode electrode. Hereinafter, α-NPD represented by the formula [1] was formed in a thickness of 500 mm as a transport layer under the same conditions as in Example 1, and a coumarin represented by the formula [3] was formed thereon as a light emitting layer. 6 (1.0 wt%) and an Alq3 co-deposited film represented by the formula [2] were formed to a thickness of 300 mm. Next, 200 liters of bathophenanthroline represented by the formula [4] was formed as an electron transport layer, and the deposition rate was adjusted so that bathophenanthroline and potassium tetraphenylborate were mixed in a ratio of 9: 1. The electron injecting material was deposited to a thickness of 300 mm by adjustment.
続いて、このように有機化合物層まで成膜した基板を、DCスパッタ装置[大阪真空製]へ移動させ、前記有機化合物層上にインジウム錫酸化物(ITO)をスパッタ法にて2000Å成膜し、透明な発光取り出し陰極電極を得た。スパッタガスとしてアルゴンと酸素の混合ガス(体積比でアルゴン:酸素=200:1)を用い、圧力を0.3Pa、DC出力を40Wとした。 Subsequently, the substrate on which the organic compound layer was formed in this way was moved to a DC sputtering apparatus [manufactured by Osaka Vacuum Co., Ltd.], and 2000 mm of indium tin oxide (ITO) was formed on the organic compound layer by sputtering. A transparent light emitting cathode electrode was obtained. A mixed gas of argon and oxygen (volume ratio: argon: oxygen = 200: 1) was used as the sputtering gas, the pressure was 0.3 Pa, and the DC output was 40 W.
このようにして、基板上に、反射型の陽極電極、正孔注入層、正孔輸送層、発光層、電子輸送層、有機化合物層および透明陰極電極を設けたトップエミッション型発光素子を得た。 In this way, a top emission type light emitting device having a reflective anode electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an organic compound layer and a transparent cathode electrode on a substrate was obtained. .
得られた素子を20mA/cm2で駆動したところ、6.3Vの電圧を示し、約2250cd/m2の緑色発光が得られ、発光効率は5.6lm/W、外部量子効率は3.3%であった。 When the obtained device was driven at 20 mA / cm 2, it showed a voltage of 6.3 V, green light emission of about 2250 cd / m 2 was obtained, the light emission efficiency was 5.6 lm / W, and the external quantum efficiency was 3.3. %Met.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約500時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 500 hours.
(実施例5)
実施例4で、電子輸送層として式[4]に示したバソフェナントロリンを400Å成膜し、更に電子注入層としてテトラフェニルホウ酸カリウムを30Åの厚さに成膜した以外は実施例4と同じ構成のトップエミッション型素子を作成した。
(Example 5 )
In Example 4, was 400Å deposited bathophenanthroline shown in Formula [4] as an electron transport layer, the same as in Example 4 except that further deposited potassium tetraphenylborate to a thickness of 30Å as an electron injection layer A top-emission element with a configuration was created.
得られた素子を20mA/cm2で駆動したところ、7.5Vの電圧を示し、約1900cd/m2の緑色発光が得られ、発光効率は4.0lm/W、外部量子効率は2.8%であった。 When the obtained device was driven at 20 mA / cm 2, it showed a voltage of 7.5 V, green light emission of about 1900 cd / m 2 was obtained, the light emission efficiency was 4.0 lm / W, and the external quantum efficiency was 2.8. %Met.
参考例1の条件で素子を定電流駆動させたところ、初期輝度が半減するまでに要した時間は約550時間であった。 When the element was driven at a constant current under the conditions of Reference Example 1, the time required for the initial luminance to be halved was about 550 hours.
(実施例6)
本発明は高分子材料を用いた素子への適用例を示す。
(Example 6 )
The present invention shows an application example to an element using a polymer material.
基板上にクロム(Cr)をDCスパッタ法にて2000Åの膜厚で成膜し、陽極電極を得た。スパッタガスとしてアルゴンガスを用い、圧力を0.2Pa、DC出力を300Wとした。その後、前記基板をUV/オゾン洗浄した後、陽極電極であるクロム(Cr)の上に高分子正孔輸送層としてPoly(3,4−ethylenedioxythiophene)/poly(styrenesulfonate)(以下、PEDOT/PSSと記す)溶液をスピンコート法で550オングストロームの厚みに成膜した。スピンコート条件は1000rpmで3分間、乾燥条件は150℃で1時間、−760mmHgに減圧しながら行った。次いでPEDOT/PSSが形成された面に、高分子電子輸送層兼発光層としてpoly(2−methoxy,5−(2’−ethyl−hexoxy)−1,−phenylene−vinylene)(以下、MEH−PPVと記す)溶液を滴下し、2000rpm/1分間の条件でスピンコートしたのち、120℃で30分間、−760mmHgに減圧しながら乾燥して積層した。得られたMEH−PPVの膜の厚みは1200Åであった。次いでこの基板を蒸着機に移し、MEH−PPV層の上に電子注入層としてテトラフェニルホウ酸カリウムを30Åの厚さに蒸着成膜した。更にこの基板をDCスパッタ装置[大阪真空製]へ移動させ、実施例9の条件で電子注入層上にインジウム錫酸化物(ITO)をスパッタ法にて2000Å成膜し、透明な発光取り出し陰極電極を得た。以上のようにして、基板上に、反射型の陽極電極、高分子正孔輸送層、高分子電子輸送・発光層、電子注入層および透明陰極電極を設けたトップエミッション型発光素子が得られた。 Chromium (Cr) was deposited on the substrate by DC sputtering to a thickness of 2000 mm to obtain an anode electrode. Argon gas was used as the sputtering gas, the pressure was 0.2 Pa, and the DC output was 300 W. Then, after UV / ozone cleaning of the substrate, Poly (3,4-ethylenedithiothiophene) / poly (styresulfonate) (hereinafter referred to as PEDOT / PSS) as a polymer hole transport layer on chromium (Cr) as an anode electrode The solution was formed to a thickness of 550 Å by spin coating. The spin coating conditions were 1000 rpm for 3 minutes, the drying conditions were 150 ° C. for 1 hour, and the pressure was reduced to −760 mmHg. Next, on the surface on which PEDOT / PSS is formed, poly (2-methoxy, 5- (2′-ethyl-hexoxy) -1, -phenylene-vinylene) (hereinafter, MEH-PPV) is used as a polymer electron transport layer and a light-emitting layer. The solution was added dropwise, spin-coated under the condition of 2000 rpm / 1 minute, and then dried and laminated at 120 ° C. for 30 minutes while reducing the pressure to −760 mmHg. The thickness of the obtained MEH-PPV film was 1200 mm. Next, the substrate was transferred to a vapor deposition machine, and potassium tetraphenylborate was deposited as an electron injection layer on the MEH-PPV layer to a thickness of 30 mm. Further, this substrate was moved to a DC sputtering apparatus [manufactured by Osaka Vacuum Co., Ltd.] and 2000 mm of indium tin oxide (ITO) was formed on the electron injection layer by sputtering under the conditions of Example 9 to obtain a transparent light emitting cathode electrode. Got. As described above, a top emission type light emitting device in which a reflective anode electrode, a polymer hole transport layer, a polymer electron transport / light emitting layer, an electron injection layer, and a transparent cathode electrode were provided on a substrate was obtained. .
この素子を20mA/cm2で駆動したところ、6.8Vの電圧を示し、約480cd/m2の赤橙色発光が得られ、発光効率は1.1lm/W、外部量子効率は2.4%であった。この素子を参考例1の条件で定電流駆動させたところ、初期輝度が半減するまでに要した時間は約200時間であった。 When this element was driven at 20 mA / cm 2, it showed a voltage of 6.8 V, reddish-orange light emission of about 480 cd / m 2 was obtained, the light emission efficiency was 1.1 lm / W, and the external quantum efficiency was 2.4%. Met. When this element was driven at a constant current under the conditions of Reference Example 1, it took about 200 hours to reduce the initial luminance by half.
本発明の電子注入材料は高分子有機発光素子に於いても十分な電子注入性を示していた。また、本実施例では本発明の電子注入材料による層を蒸着法にて形成したが、予め高分子電子輸送性材料に本発明の電子注入材料を溶解・分散して膜形成し、電子輸送層と電子注入層を兼ねる構成をとることもできる。 The electron injecting material of the present invention has shown sufficient electron injecting property even in a polymer organic light emitting device. Further, in this example, the layer of the electron injection material of the present invention was formed by vapor deposition, but the electron injection material of the present invention was dissolved and dispersed in advance in a polymer electron transport material to form a film. In addition, a structure that doubles as an electron injection layer can also be employed.
1 基板
2 陽極
3 発光層
4 電子注入層
5 陰極
6 ホール輸送層
7 電子輸送層
8 ホール注入層
9 ホール/エキシトンブロッキング層
DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Light emitting layer 4 Electron injection layer 5 Cathode 6 Hole transport layer 7 Electron transport layer 8 Hole injection layer 9 Hole / exciton blocking layer
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