JPH05179239A - Organic thin-film luminescent element - Google Patents
Organic thin-film luminescent elementInfo
- Publication number
- JPH05179239A JPH05179239A JP14466192A JP14466192A JPH05179239A JP H05179239 A JPH05179239 A JP H05179239A JP 14466192 A JP14466192 A JP 14466192A JP 14466192 A JP14466192 A JP 14466192A JP H05179239 A JPH05179239 A JP H05179239A
- Authority
- JP
- Japan
- Prior art keywords
- group
- injection layer
- light emitting
- organic thin
- general formula
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 22
- -1 diamine compound Chemical class 0.000 claims abstract description 11
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract 5
- 238000002347 injection Methods 0.000 claims description 36
- 239000007924 injection Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 15
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- 125000003545 alkoxy group Chemical group 0.000 claims 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims 3
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- ZBJJDYGJCNTNTH-UHFFFAOYSA-N Betahistine mesilate Chemical group CS(O)(=O)=O.CS(O)(=O)=O.CNCCC1=CC=CC=N1 ZBJJDYGJCNTNTH-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 abstract 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 abstract 1
- 239000010408 film Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 238000007740 vapor deposition Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical class C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000891 luminescent agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical class C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- WSRHMJYUEZHUCM-UHFFFAOYSA-N perylene-1,2,3,4-tetracarboxylic acid Chemical class C=12C3=CC=CC2=CC=CC=1C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C2=C1C3=CC=C2C(=O)O WSRHMJYUEZHUCM-UHFFFAOYSA-N 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は有機薄膜発光素子の正
孔注入層に係り、特に成膜性に優れる発光素子の正孔注
入層に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hole injecting layer of an organic thin film light emitting device, and more particularly to a hole injecting layer of a light emitting device having excellent film forming properties.
【０００２】[0002]
【従来の技術】従来のブラウン管に代わるフラットディ
スプレイの需要の急増に伴い、各種表示素子の開発及び
実用化が精力的に進められている。エレクトロルミネッ
センス素子（以下ＥＬ素子とする）もこうしたニ−ズに
即するものであり、特に全固体の自発発光素子として、
他のディスプレイにはない高解像度及び高視認性により
注目を集めている。現在、実用化されているものは、発
光層にＺｎＳ／Ｍｎ系を用いた無機材料からなるＥＬ素
子である。しかるに、この種の無機ＥＬ素子は発光に必
要な駆動電圧が２００Ｖ程度と高いため駆動方法が複雑
となり製造コストが高いといった問題点がある。また、
青色発光の効率が低いため、フルカラ−化が困難であ
る。2. Description of the Related Art With the rapid increase in demand for flat displays replacing conventional cathode ray tubes, various display elements have been vigorously developed and put into practical use. An electroluminescence element (hereinafter referred to as an EL element) is also adapted to such a need, and in particular, as an all solid state spontaneous light emitting element,
It attracts attention due to its high resolution and high visibility that other displays do not have. At present, what has been put into practical use is an EL element made of an inorganic material using a ZnS / Mn-based light emitting layer. However, this type of inorganic EL element has a problem that the driving method is complicated and the manufacturing cost is high because the driving voltage required for light emission is as high as about 200V. Also,
Since the efficiency of blue light emission is low, it is difficult to achieve full color.
【０００３】これに対して、有機材料を用いた薄膜発光
素子は、発光に必要な駆動電圧が大幅に低減でき、かつ
各種発光材料の添加によりフルカラ−化の可能性を充分
にもつことから、近年研究が活発化している。特に電極
／正孔注入層／発光層からなる積層型において、発光剤
にトリス（８−ヒドロキシキノリン）アルミニウム、正
孔注入剤に１，１’−ビス（４−Ｎ，Ｎ−ジトリアミノ
フェニル）シクロヘキサンを用いることにより、１０Ｖ
以下の印加電圧で１０００ｃｄ／ｍ2 以上高輝度が得ら
れたという報告がなされて以来開発に拍車がかけられた
（Appl.Phys.Lett. 51, 913,(1987)) 。On the other hand, a thin-film light emitting device using an organic material can drastically reduce a driving voltage required for light emission, and has a possibility of being fully colored by adding various light emitting materials. Research has become active in recent years. In particular, in the laminated type composed of electrode / hole injection layer / light emitting layer, tris (8-hydroxyquinoline) aluminum is used as the light emitting agent, and 1,1′-bis (4-N, N-ditriaminophenyl) is used as the hole injection agent. 10V by using cyclohexane
The development was spurred since it was reported that a high luminance of 1000 cd / m 2 or more was obtained with the following applied voltage (Appl. Phys. Lett. 51 , 913, (1987)).
【０００４】現在広く研究されている該有機発光素子の
具体的な構造ならびに材料につき、図面を使って、以下
に説明する。図１は積層構造型の典型的な構造断面図で
ある（発光は図中の矢印に示す方向に進む）。ガラス等
の透明基板１上に金、ニッケル等の半透膜やインジウム
スズ酸化物（ＩＴＯ）、酸化スズ（ＳｎＯ2 ）等の透明
導電膜からなる正極２を抵抗加熱蒸着、電子ビ−ム蒸
着、スパッタ法により形成する。該電極２は、透明性を
持たせるために、１００〜３０００Åの厚さにすること
が望ましい。次に正孔注入層３、発光層４と順次有機薄
膜を成膜する。Specific structures and materials of the organic light-emitting device which are currently widely studied will be described below with reference to the drawings. FIG. 1 is a typical structural cross-sectional view of a laminated structure type (light emission proceeds in a direction indicated by an arrow in the drawing). On a transparent substrate 1 made of glass or the like, a positive electrode 2 made of a semi-permeable film of gold or nickel or a transparent conductive film of indium tin oxide (ITO) or tin oxide (SnO 2 ) is deposited by resistance heating or electron beam deposition. Formed by sputtering. It is desirable that the electrode 2 has a thickness of 100 to 3000 Å in order to have transparency. Next, an organic thin film is sequentially formed on the hole injection layer 3 and the light emitting layer 4.
【０００５】正孔注入物質としては、上記１，１’−ビ
ス（４−Ｎ，Ｎ−ジトリアミノフェニル）シクロヘキサ
ン等のジアミン系化合物の他に、ヒドラゾン系化合物、
スチルベン系化合物等が用いられている。また、発光物
質には、上記トリス（８−ヒドロキシキノリン）アルミ
ニウム等の金属錯体化合物の他に、ジスチリルベンゼン
化合物、ペリレン系化合物等が用いられている。両層と
もにスピンコ−ト、キャスティング、ＬＢ法、抵抗加熱
蒸着、電子ビ−ム蒸着等により成膜できるが、現在のと
ころ発光特性が優れていることから抵抗加熱蒸着法が主
流である。また、両層の膜厚は、抵抗加熱蒸着法におい
ては、それぞれ２００〜３０００Å、好適には３００〜
１５００Åである。最後に負極５を蒸着にて形成する。
なお、電極５用の材料としては仕事関数の小さいＭｇ，
Ｍｇ／Ａｇ，Ｉｎ，Ｃａ，Ａｌ等が用いられる。有機薄
膜素子には電源６を介して直流電圧が印加される。As the hole injecting substance, in addition to diamine compounds such as 1,1'-bis (4-N, N-ditriaminophenyl) cyclohexane, hydrazone compounds,
Stilbene compounds are used. In addition to the metal complex compound such as tris (8-hydroxyquinoline) aluminum, a distyrylbenzene compound, a perylene-based compound or the like is used as a light emitting substance. Both layers can be formed by spin coating, casting, LB method, resistance heating vapor deposition, electron beam vapor deposition and the like, but at present the resistance heating vapor deposition method is the mainstream because of its excellent light emitting characteristics. Further, the film thickness of both layers is 200 to 3000 Å, preferably 300 to 300 in the resistance heating vapor deposition method.
It is 1500Å. Finally, the negative electrode 5 is formed by vapor deposition.
As the material for the electrode 5, Mg having a small work function,
Mg / Ag, In, Ca, Al or the like is used. A DC voltage is applied to the organic thin film element via the power supply 6.
【０００６】図２は他の素子構造をしめす断面図であ
る。（発光は図の矢印に示す方向に進む）。ガラス等の
透明基板１上に金、ニッケル等の半透膜やインジウムス
ズ酸化物（ＩＴＯ）、酸化スズ（ＳｎＯ2 ）等の透明導
電膜からなる正極２を、図１と同様に形成し、正孔注入
層３，発光層４さらに電子注入層７の３層を成膜する。
電子注入剤については、ジフェノキノン系化合物、ペリ
レン系化合物、オキサジアゾ−ル系化合物等が用いられ
ている。該正孔注入層３，発光層４および電子注入層７
の膜厚はすべて上記図１の場合と同様にそれぞれ２００
〜３０００Å、好適には３００〜１５００Åである。最
後に負極５をＭｇ，Ｍｇ／Ａｇ，Ｉｎ，Ｃａ，Ａｌ等を
用いて蒸着する。FIG. 2 is a sectional view showing another element structure. (Light emission proceeds in the direction indicated by the arrow in the figure). On a transparent substrate 1 made of glass or the like, a positive electrode 2 made of a semi-permeable film made of gold or nickel or a transparent conductive film made of indium tin oxide (ITO) or tin oxide (SnO 2 ) is formed in the same manner as in FIG. The three layers of the hole injection layer 3, the light emitting layer 4 and the electron injection layer 7 are formed.
As the electron injecting agent, diphenoquinone compounds, perylene compounds, oxadiazol compounds and the like are used. The hole injection layer 3, the light emitting layer 4 and the electron injection layer 7
The film thickness of each is 200 as in the case of FIG. 1 above.
˜3000 Å, preferably 300 to 1500 Å. Finally, the negative electrode 5 is vapor-deposited using Mg, Mg / Ag, In, Ca, Al or the like.
【０００７】[0007]
【発明が解決しようとする課題】この様に、有機材料を
用いた薄膜発光素子は低電圧駆動やフルカラ−化の可能
性等を強く示唆しているものの、性能面で解決しなけれ
ばならない課題が多く残されている。特に１万時間程度
の長時間駆動に伴う特性劣化の問題は乗り越えなければ
ならないハ−ドルである。また、該有機薄膜の膜厚は１
μｍ以下であるため、成膜性が良好で、成膜中にピンホ
−ル等の電気的欠陥を生じないこと、さらには、薄膜で
あるがために、発光時に素子に加わる電界及び／または
電流により短絡しない様な材料開発および成膜法の検討
が必要である。特に、抵抗加熱蒸着膜においては電気的
欠陥が発生しやすく、かつ発光時に短絡しやすいといっ
た問題がある。さらには、量産性の観点から、大量製造
が容易で安価な有機材料の開発や素子形成方法の改良等
も重要な技術課題である。As described above, although the thin film light emitting device using an organic material strongly suggests the possibility of low voltage driving and full colorization, there is a problem to be solved in terms of performance. There are many left. In particular, the problem of characteristic deterioration due to long-time driving of about 10,000 hours is a hardware that must be overcome. The thickness of the organic thin film is 1
Since it is less than or equal to μm, the film forming property is good, and electrical defects such as pinholes do not occur during film formation. Furthermore, since it is a thin film, the electric field and / or current applied to the element during light emission. Therefore, it is necessary to study the material development and film formation method so that short circuit will not occur. In particular, the resistance heating vapor deposition film has problems that electrical defects are likely to occur and that a short circuit is likely to occur during light emission. Further, from the viewpoint of mass productivity, development of an organic material which is easy to mass-produce and is inexpensive, improvement of a device forming method, and the like are important technical subjects.
【０００８】この発明は上述の点に鑑みてなされその目
的は樹脂分散成膜におけるバインダを開発することによ
り成膜性に優れる有機薄膜発光素子を提供することにあ
る。The present invention has been made in view of the above points, and an object thereof is to provide an organic thin film light emitting device having excellent film forming properties by developing a binder for resin dispersion film formation.
【０００９】[0009]
【課題を解決するための手段】上述の目的はこの発明に
よれば、正極と負極とからなる一対の電極と、その間に
はさまれた発光層と電荷注入層とを有し、電荷注入層は
電子注入層と正孔注入層のうちの少なくとも正孔注入層
からなり、この際正孔注入層は正孔注入物質とポリビニ
ルカルバゾール樹脂からなるとする事により達成され
る。According to the present invention, there is provided a charge injection layer having a pair of electrodes consisting of a positive electrode and a negative electrode, a light emitting layer and a charge injection layer sandwiched therebetween. Is formed of at least a hole injection layer of an electron injection layer and a hole injection layer, and the hole injection layer is formed of a hole injection material and a polyvinylcarbazole resin.
【００１０】ジアミン系化合物の具体例が化学式Ｉ−１
ないし化学式Ｉ−２３にヒドラゾン系化合物が化学式II
−１ないし化学式II−８にスチルベン系化合物が化学式
III-１ないし化学式III-４に示される。Specific examples of the diamine compounds are represented by the chemical formula I-1.
Or a hydrazone-based compound in Formula I-23
-1 to the formula II-8, the stilbene compound is a chemical formula
It is shown in III-1 to Formula III-4.
【００１１】[0011]
【化５】 [Chemical 5]
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】[0013]
【化７】 [Chemical 7]
【００１４】[0014]
【化８】 [Chemical 8]
【００１５】[0015]
【化９】 [Chemical 9]
【００１６】[0016]
【化１０】 [Chemical 10]
【００１７】[0017]
【作用】正孔注入物質とポリビニルカルバゾール樹脂バ
インダの分散膜を用いることにより良好な膜を形成可能
で膜中にピンホール等の電気的欠陥が少ない。また発光
時に素子にかかる電界または電流により発生する短絡現
象がなくなる。正孔注入物質にジアミン系化合物、ヒド
ラゾン系化合物、およびスチルベン化合物が良好な結果
をもたらす。[Function] By using the dispersion film of the hole injecting substance and the polyvinylcarbazole resin binder, a good film can be formed, and the number of electrical defects such as pinholes in the film is small. In addition, the short circuit phenomenon caused by the electric field or current applied to the element during light emission is eliminated. Diamine-based compounds, hydrazone-based compounds, and stilbene compounds provide good results for the hole injection materials.
【００１８】[0018]
【実施例】つぎにこの発明の実施例を図面を用いて説明
する。正孔注入物質とポリビニルカルバゾールからなる
分散膜は、両者を適当な有機溶媒中に溶解せしめてなる
塗液を用いて、スピンコート、キャスティング等により
形成される。塗液の配合時における正孔注入物質の全量
に占める重量比は３０乃至８０％、好適には４０乃至７
０％である。また正孔注入層分散膜の膜厚は５００乃至
３０００Å、好適には８００乃至２０００Åである。Embodiments of the present invention will now be described with reference to the drawings. The dispersion film composed of the hole injection material and polyvinylcarbazole is formed by spin coating, casting or the like using a coating solution prepared by dissolving both of them in an appropriate organic solvent. The weight ratio of the hole injecting material to the total amount of the coating solution is 30 to 80%, preferably 40 to 7
It is 0%. The thickness of the hole injection layer dispersion film is 500 to 3000Å, preferably 800 to 2000Å.
【００１９】実施例１ 膜厚〜１０００ÅのＩＴＯを設けた５０ｍｍ角のガラス
を基板とし該基板をスピンコ−タにセットした後、前記
ジアミン系化合物のうちＩ−１で示した化合物１重量
部、ポリビニルカルバゾール樹脂１重量部をジクロロメ
タン５００重量部にて溶解させた塗液を用いて、回転数
５０００ｒｐｍにて該基板上に〜１０００Åスピンコ−
トし、正孔注入層とした。次に該正孔注入層をコ−トし
た基板を抵抗加熱蒸着装置内にセットし、発光層を形成
した。成膜に際して、真空槽内は６×１０-6Ｔｏｒｒま
で減圧した。発光剤には、（８−ヒドロキシキノリン）
アルミニウムを用い、ボ−ト温度１００〜３００0 Ｃの
範囲で加熱し、成膜速度を２Å／秒の条件下で６００Å
形成した。最後に、試料を真空槽から取り出し、直径５
ｍｍのドットパタ−ン１６個からなるステンレス製マス
クを取りつけ、新たに抵抗加熱蒸着装置内にセットし負
極としてＭｇ／Ａｇ（１０：１の比率）を形成した。Example 1 A glass of 50 mm square provided with ITO having a film thickness of 1000 Å was used as a substrate, and the substrate was set on a spin coater. Using a coating solution prepared by dissolving 1 part by weight of polyvinylcarbazole resin in 500 parts by weight of dichloromethane, a spin coater of about 1000 Å was applied on the substrate at a rotation speed of 5000 rpm.
As a hole injection layer. Next, the substrate coated with the hole injection layer was set in a resistance heating vapor deposition device to form a light emitting layer. During film formation, the pressure inside the vacuum chamber was reduced to 6 × 10 −6 Torr. The luminescent agent is (8-hydroxyquinoline)
Using aluminum, ball - heated in the range of bets temperature 100 to 300 0 C, 600 Å and the deposition rate under the conditions of 2 Å / sec
Formed. Finally, remove the sample from the vacuum chamber and
A stainless steel mask consisting of 16 mm dot patterns was attached, and the mask was newly set in a resistance heating vapor deposition device to form Mg / Ag (ratio of 10: 1) as a negative electrode.
【００２０】実施例２ 実施例１と同様に膜厚〜１０００ÅのＩＴＯを設けた５
０ｍｍ角のガラスを基板に用い実施例１と同一材料、同
一製法、同一条件下で正孔注入層と発光層を形成する。
次に、発光層形成後、真空槽の真空を破らず、続けて電
子注入層として下記（IV）に構造式を示したペリレンテ
トラカルボン酸誘導体を、ボ−ト加熱温度１５０〜３０
０℃、成膜速度３Å／秒の条件下で７００Å形成した。
最後に、上記実施例１と同様に、試料を真空槽から取り
出し、直径５ｍｍのドットパタ−ン１６個からなるステ
ンレス製マスクを取りつけ、新たに抵抗加熱蒸着装置内
にセットし負極としてＭｇ／Ａｇ（１０：１の比率）を
形成した。Example 2 As in Example 1, ITO having a film thickness of 1000 Å was provided 5
The hole injection layer and the light emitting layer are formed using the same material, the same manufacturing method, and the same conditions as in Example 1 by using 0 mm square glass as the substrate.
Next, after forming the light emitting layer, the vacuum of the vacuum chamber was not broken, and the perylene tetracarboxylic acid derivative having the structural formula (IV) shown below was continuously used as an electron injecting layer at a boat heating temperature of 150 to 30.
700 Å was formed under the conditions of 0 ° C. and a film forming rate of 3 Å / sec.
Finally, as in Example 1 above, the sample was taken out of the vacuum chamber, a stainless steel mask consisting of 16 dot patterns with a diameter of 5 mm was attached, and the sample was newly set in the resistance heating vapor deposition apparatus and Mg / Ag (as a negative electrode). 10: 1 ratio) was formed.
【００２１】[0021]
【化１１】 [Chemical 11]
【００２２】以上に示した２つの実施例における有機薄
膜発光素子に、直流電圧を印加したところ、ともに緑色
（発光中心波長：５５０ｎｍ）の均一な発光が得られ
た。また、ともに該５０ｍｍ角のガラス基板上の直径５
ｍｍのドットパタ−ン１６個のパタ−ンすべてが、短絡
現象をおこさず、発光特性のばらつき５％の範囲内にお
さまった。さらに、実施例１の素子においては、印加電
圧１５Ｖ下で、２０００ｃｄ／ｍ2 （電流密度１００ｍ
Ａ／ｃｍ2 ）、実施例２の素子においては、印加電圧１
５Ｖ下で、１８００ｃｄ／ｍ2 （電流密度８０ｍＡ／ｃ
ｍ2 ）の高輝度発光が得られた。When a DC voltage was applied to the organic thin film light emitting devices in the above two examples, uniform green (light emission center wavelength: 550 nm) light emission was obtained. Also, both have a diameter of 5 mm on the glass substrate of 50 mm square.
All 16 16 mm dot patterns did not cause a short circuit phenomenon, and the variation of the light emission characteristics was within the range of 5%. Furthermore, in the device of Example 1, under an applied voltage of 15 V, 2000 cd / m 2 (current density 100 m
A / cm 2 ), in the device of Example 2, an applied voltage of 1
Under 5 V, 1800 cd / m 2 (current density 80 mA / c
High-luminance light emission of m 2 ) was obtained.
【００２３】実施例３ 正孔注入物質に前記ヒドラゾン系化合物のうちII−６を
用いて、その他の材料製法、条件は実施例１と同一にし
て素子を形成した。上記実施例における有機発光素子
に、直流電圧を印加したところ、緑色（発光中心波長：
５５０ｎｍ）の均一な発光が得られた。また、該５０ｍ
ｍ角のガラス基板上の直径５ｍｍのドットパタ−ン１６
個のパタ−ンすべてが、短絡現象をおこさず、発光特性
ばらつき±７％の範囲内におさまった。さらに、印加電
圧１５Ｖ下で、１４００ｃｄ／ｍ2 （電流密度１２０ｍ
Ａ／ｃｍ2 ）の高輝度発光が得られた。Example 3 A device was formed by using II-6 of the hydrazone compounds as the hole injecting material and using the same method and conditions as in Example 1 except for the other materials. When a DC voltage was applied to the organic light emitting device in the above example, green (light emission center wavelength:
A uniform emission of 550 nm) was obtained. Also, the 50m
Dot pattern 16 with a diameter of 5 mm on an m-square glass substrate 16
All the individual patterns did not cause the short circuit phenomenon, and the variation in the light emission characteristics was within ± 7%. Furthermore, under an applied voltage of 15 V, 1400 cd / m 2 (current density 120 m
A high-luminance light emission of A / cm 2 ) was obtained.
【００２４】実施例４ 正孔注入物質に前記スチルベン系化合物のうちIII-２を
用いて、その他の材料製法、条件は実施例１と同一にし
て素子を形成した。上記実施例における有機発光素子
に、直流電圧を印加したところ、緑色（発光中心波長
：５５０ｎｍ）の均一な発光が得られた。また、該５
０ｍｍ角のガラス基板上の直径５ｍｍのドットパタ−ン
１６個のパタ−ンすべてが、短絡現象をおこさず、発光
特性ばらつき±７％の範囲内におさまった。さらに、印
加電圧１５Ｖ下で、１５００ｃｄ／ｍ 2 （電流密度１１
０ｍＡ／ｃｍ2 ）の高輝度発光が得られた。Example 4 Among the stilbene compounds, III-2 was used as the hole injecting material.
The other materials were manufactured in the same manner as in Example 1, except that the conditions were the same.
To form an element. Organic light-emitting device in the above example
When a DC voltage was applied to the
: 550 nm) was obtained. Also, the 5
Dot pattern with a diameter of 5 mm on a 0 mm square glass substrate
All 16 patterns emit light without causing short circuit
Characteristic variation was within ± 7%. Furthermore, the mark
1500 cd / m under applied voltage of 15 V 2(Current density 11
0 mA / cm2) High-luminance light emission was obtained.
【００２５】[0025]
【発明の効果】この発明によれば、正極と負極とからな
る一対の電極と、その間にはさまれた発光層と電荷注入
層とを有し、電荷注入層は電子注入層と正孔注入層のう
ちの少なくとも正孔注入層からなり、この際正孔注入層
は正孔注入物質とポリビニルカルバゾール樹脂からなる
とするので、良好な膜形成可能で、膜中に発生するピン
ホ−ル等の電気的欠陥が少なく、発光時に素子にかかる
電界およびまたは電流により発生する短絡現象を防ぐこ
とができ、高輝度発光性に優れる有機薄膜発光素子が得
られる。According to the present invention, a pair of electrodes consisting of a positive electrode and a negative electrode, a light emitting layer and a charge injection layer sandwiched between the electrodes are provided, and the charge injection layer is an electron injection layer and a hole injection layer. Of the layers, at least the hole injection layer is formed. In this case, since the hole injection layer is composed of the hole injection material and the polyvinylcarbazole resin, it is possible to form a good film, and to generate an electric charge such as pinholes generated in the film. It is possible to obtain an organic thin film light emitting device which has a small number of optical defects, can prevent a short circuit phenomenon caused by an electric field and / or a current applied to the device during light emission, and is excellent in high-luminance light emission.
【図１】積層構造型の素子の構造を示す断面図FIG. 1 is a cross-sectional view showing the structure of a laminated structure type element.
【図２】積層構造型の素子の他の構造をしめす断面図FIG. 2 is a cross-sectional view showing another structure of a laminated structure type element.
１ 絶縁性透明性基板 ２ 正極 ３ 正孔注入層 ４ 発光層 ５ 負極 ６ 電源 ７ 電子注入層 1 Insulating Transparent Substrate 2 Positive Electrode 3 Hole Injection Layer 4 Light Emitting Layer 5 Negative Electrode 6 Power Supply 7 Electron Injection Layer
Claims (4)
間にはさまれた発光層と電荷注入層とを有し、 電荷注入層は電子注入層と正孔注入層のうちの少なくと
も正孔注入層からなり、この際正孔注入層は正孔注入物
質とポリビニルカルバゾール樹脂からなることを特徴と
する有機薄膜発光素子。1. A pair of electrodes consisting of a positive electrode and a negative electrode, and a light emitting layer and a charge injection layer sandwiched therebetween, wherein the charge injection layer is at least a positive electrode injection layer or a hole injection layer. An organic thin film light emitting device comprising a hole injection layer, wherein the hole injection layer comprises a hole injection material and a polyvinylcarbazole resin.
質は一般式（Ｉ）で示されるジアミン系化合物であるこ
とを特徴とする有機薄膜発光素子。 【化１】 （一般式（Ｉ）においてＡは下記一般式（IA），（IB)
又は（IC) で示される。 【化２】 Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 は、置換されてもよいアルキル
基，アリル基，アリ−ル基，アラルキル基である。また
一般式（IA），（IB) 又は（IC) においてＲ5 、Ｒ6 、
Ｒ7 、Ｒ8 は水素原子，ハロゲン，置換されてもよいア
ルキル基，アルコキシ基、Ｘは−Ｃ（Ｒ9 ）（Ｒ10）−
（Ｒ9 、Ｒ10は水素原子，アルキル基），─Ｏ─，─Ｓ
─，＞Ｃ6 Ｈ10である。）2. The organic thin film light emitting device according to claim 1, wherein the hole injecting substance is a diamine compound represented by the general formula (I). [Chemical 1] (In the general formula (I), A is the following general formula (IA), (IB)
Or (IC). [Chemical 2] R 1 , R 2 , R 3 and R 4 are an alkyl group, an allyl group, an aryl group and an aralkyl group which may be substituted. In the general formula (IA), (IB) or (IC), R 5 , R 6 ,
R 7 and R 8 are hydrogen atoms, halogens, optionally substituted alkyl groups and alkoxy groups, and X is —C (R 9 ) (R 10 ) —.
(R 9 and R 10 are hydrogen atoms and alkyl groups), --O--, --S
─,> it is a C 6 H 10. )
質は一般式（II）で示されるヒドラゾン系化合物である
ことを特徴とする有機薄膜発光素子。 【化３】 （ Ｒ11は、水素原子，アルキル基，ハロゲン原子，ア
ルコキシ基をあらわし、Ｒ12、Ｒ13は、置換されてもよ
いアルキル基，アリ−ル基，アラルキル基、Ｒ14、Ｒ15
は置換されてもよいアルキル基，アリ−ル基，アラルキ
ル基，テニル基である。）3. The organic thin film light emitting device according to claim 1, wherein the hole injecting substance is a hydrazone compound represented by the general formula (II). [Chemical 3] (R 11 represents a hydrogen atom, an alkyl group, a halogen atom or an alkoxy group, and R 12 and R 13 represent an optionally substituted alkyl group, aryl group, aralkyl group, R 14 and R 15
Is an optionally substituted alkyl group, aryl group, aralkyl group, or tenyl group. )
質は一般式（III ）で示されるスチルベン系化合物であ
ることを特徴とする有機薄膜発光素子。 【化４】 （Ｒ16は、水素原子，アルキル基，ハロゲン基，アルコ
キシ基を表しＲ17、Ｒ18は、置換されてもよいアリ−ル
基，アラルキル基を表しＲ19、Ｒ20は、置換されてもよ
いアリ−ル基である。）4. The organic thin film light emitting device according to claim 1, wherein the hole injecting substance is a stilbene compound represented by the general formula (III). [Chemical 4] (R 16 represents a hydrogen atom, an alkyl group, a halogen group or an alkoxy group, R 17 and R 18 represent an aryl group or an aralkyl group which may be substituted, and R 19 and R 20 may be substituted. It is a good aryl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14466192A JPH05179239A (en) | 1991-09-09 | 1992-06-05 | Organic thin-film luminescent element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22754991 | 1991-09-09 | ||
| JP3-227549 | 1991-09-09 | ||
| JP14466192A JPH05179239A (en) | 1991-09-09 | 1992-06-05 | Organic thin-film luminescent element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05179239A true JPH05179239A (en) | 1993-07-20 |
Family
ID=26476015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14466192A Pending JPH05179239A (en) | 1991-09-09 | 1992-06-05 | Organic thin-film luminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05179239A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080014464A1 (en) * | 2006-06-22 | 2008-01-17 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent device using aryl amine derivative containing heterocycle |
| JP2012212726A (en) * | 2011-03-30 | 2012-11-01 | Sony Corp | Ink composition for reverse printing, printing method using the same and manufacturing method of display device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01243393A (en) * | 1988-03-24 | 1989-09-28 | Nec Corp | Organic thin-film luminescent device and manufacture thereof |
| JPH02235983A (en) * | 1989-03-09 | 1990-09-18 | Idemitsu Kosan Co Ltd | Thin-film electroluminescent element |
| JPH042096A (en) * | 1989-10-20 | 1992-01-07 | Asahi Chem Ind Co Ltd | Coating type organic el element |
| JPH0485389A (en) * | 1990-07-26 | 1992-03-18 | Ricoh Co Ltd | Electroluminescent element |
-
1992
- 1992-06-05 JP JP14466192A patent/JPH05179239A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01243393A (en) * | 1988-03-24 | 1989-09-28 | Nec Corp | Organic thin-film luminescent device and manufacture thereof |
| JPH02235983A (en) * | 1989-03-09 | 1990-09-18 | Idemitsu Kosan Co Ltd | Thin-film electroluminescent element |
| JPH042096A (en) * | 1989-10-20 | 1992-01-07 | Asahi Chem Ind Co Ltd | Coating type organic el element |
| JPH0485389A (en) * | 1990-07-26 | 1992-03-18 | Ricoh Co Ltd | Electroluminescent element |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080014464A1 (en) * | 2006-06-22 | 2008-01-17 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent device using aryl amine derivative containing heterocycle |
| US10263192B2 (en) * | 2006-06-22 | 2019-04-16 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent device using aryl amine derivative containing heterocycle |
| JP2012212726A (en) * | 2011-03-30 | 2012-11-01 | Sony Corp | Ink composition for reverse printing, printing method using the same and manufacturing method of display device |
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