JPH0665569A - Electroluminescent element - Google Patents
Electroluminescent elementInfo
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- JPH0665569A JPH0665569A JP5104993A JP10499393A JPH0665569A JP H0665569 A JPH0665569 A JP H0665569A JP 5104993 A JP5104993 A JP 5104993A JP 10499393 A JP10499393 A JP 10499393A JP H0665569 A JPH0665569 A JP H0665569A
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- Prior art keywords
- organic
- layer
- anode
- light emitting
- cathode
- Prior art date
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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、発光性物質からなる発
光層を有し、電界を印加することにより電気エネルギー
を直接光エネルギーに変換でき、従来の白熱灯、蛍光灯
あるいは発光ダイオード等とは異なり大面積の面状発光
体の実現を可能にする電界発光素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a light emitting layer made of a light emitting material and can directly convert electric energy into light energy by applying an electric field. In contrast, the present invention relates to an electroluminescent device that enables realization of a large-area planar light-emitting body.
【０００２】[0002]
【従来の技術】電界発光素子はその発光励起機構の違い
から、（１）発光層内での電子や正孔の局所的な移動に
より発光体を励起し、交流電界でのみ発光する真性電界
発光素子と、（２）電極からの電子と正孔の注入とその
発光層内での再結合により発光体を励起し、直流電界で
作動するキャリア注入型電界発光素子の二つに分けられ
る。（１）の真性電界発光型の発光素子は一般にＺｎＳ
にＭｎ、Ｃｕ等を添加した無機化合物を発光体とするも
のであるが、駆動に２００Ｖ以上の高い交流電界を必要
とすること、製造コストが高いこと、輝度や耐久性も不
十分である等の多くの問題点を有する。2. Description of the Related Art An electroluminescence device has an intrinsic electroluminescence device which emits light only in an alternating electric field by (1) exciting a light emitter by local movement of electrons and holes in a light emitting layer due to a difference in emission excitation mechanism. The element is divided into (2) a carrier injection type electroluminescent element that operates by a DC electric field by injecting electrons and holes from an electrode and recombining the electrons and holes in the light emitting layer to excite a luminescent body. The intrinsic electroluminescence type light emitting device of (1) is generally ZnS.
An inorganic compound to which Mn, Cu, etc. are added is used as a light emitter, but it requires a high AC electric field of 200 V or more for driving, high manufacturing cost, insufficient brightness and durability, etc. Has many problems.
【０００３】（２）のキャリア注入型電界発光素子は発
光層として薄膜状有機化合物を用いるようになってから
高輝度のものが得られるようになった。たとえば、特開
昭５９−１９４３９３、（米国特許４，５３９，５０
７、特開昭６３−２９５６６９５）、米国特許４，７２
０，４３２（及び特開昭６３−２６４６９２）には、陽
極、有機質ホール注入輸送帯、有機質電子注入性発光体
および陰極から成る電界発光素子が開示されており、こ
れらに使用される材料としては、例えば、有機質ホール
注入輸送用材料としては芳香族三級アミンが、また、有
機質電子注入性発光材料としては、アルミニウムトリス
オキシン等が代表的な例としてあげられる。In the carrier injection type electroluminescent device (2), a thin film organic compound has been used as a light emitting layer, and a high brightness device has been obtained. For example, JP-A-59-194393, (US Pat. No. 4,539,50
7, JP-A-63-2965695), U.S. Pat. No. 4,72.
No. 0,432 (and Japanese Patent Laid-Open No. 63-264692) discloses an electroluminescent device consisting of an anode, an organic hole injecting and transporting zone, an organic electron injecting luminescent material and a cathode. As a typical example, an aromatic tertiary amine is used as the organic hole injecting and transporting material, and aluminum trisoxine is a typical example of the organic electron injecting light emitting material.
【０００４】また、Ｊｐｎ．Ｊｏｕｒｎａｌ ｏｆ Ａ
ｐｐｌｉｅｄ Ｐｈｙｓｉｃｄ，ｖｏｌ．２７，ｐ７１
３−７１５には陽極、有機質ホール輸送層、発光層、有
機質電子輸送層および陰極から成る電界発光素子が報告
されており、これらに使用される材料としては、有機質
ホール輸送材料としてはＮ，Ｎ’−ジフェニル−Ｎ，
Ｎ’−ビス（３−メチルフェニル）−１，１’−ビフェ
ニル−４，４’−ジアミンが、また、有機質電子輸送材
料としては、３，４，９，１０−ペリレンテトラカルボ
ン酸ビスベンズイミダゾールが、また発光材料としては
フタロペリノンが例示されている。In addition, Jpn. Journal of A
applied Physicd, vol. 27, p71
3-715 reports an electroluminescent device comprising an anode, an organic hole transport layer, a light emitting layer, an organic electron transport layer and a cathode. Materials used for these are N, N as organic hole transport materials. '-Diphenyl-N,
N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, and as an organic electron transport material, 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole However, phthaloperinone is exemplified as the light emitting material.
【０００５】上記の例を含め有機化合物を発光体とする
キャリア注入型電界発光素子はその研究の歴史も浅く、
未だその材料研究やデバイス化への研究が充分になされ
ているとは言えず、現状では更なる輝度の向上、発光波
長のコントロールあるいは耐久性の向上など多くの課題
を抱えているのが実情である。The carrier injection type electroluminescent device using an organic compound as a light emitter including the above examples has a short history of research,
It cannot be said that the material research and research into devices have been sufficiently conducted, and in the present situation, there are many problems such as further improvement of brightness, control of emission wavelength or improvement of durability. is there.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記従来技
術の実情に鑑みてなされたものであり、その目的は発光
性能が長時間に亘って持続する耐久性に優れた電界発光
素子を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the circumstances of the above-mentioned prior art, and an object thereof is to provide an electroluminescent device having excellent durability in which light emitting performance is maintained for a long time. To do.
【０００７】[0007]
【課題を解決するための手段】本発明によれば、陽極お
よび陰極と、これらの間に狭持された一層または複数層
の有機化合物層より構成される電界発光素子において、
前記有機化合物層のうち少なくとも一層が、下記一般式
〔Ｉ〕（化１）で表わされるオキサジアゾール系化合物
を構成成分とする層であることを特徴とする電界発光素
子が提供される。また、陽極と陰極との間に、有機ホー
ル輸送層と、有機発光層と、有機電子輸送層とが陽極側
から順に形成された有機３層素子構造、或いは陽極と陰
極との間に、有機発光層と、有機電子輸送層とが陽極側
から順に形成された有機２層素子構造を有する電界発光
素子において、前記有機電子輸送層が下記一般式〔Ｉ〕
（化１）で表わされるオキサジアゾール系化合物を構成
成分とすることを特徴とする電界発光素子が提供され
る。更に、陽極と陰極との間に、有機ホール輸送層と、
有機発光層と、有機電子輸送層とが陽極側から順に形成
された有機３層素子構造、或いは陽極と陰極との間に、
有機ホール輸送層と、有機発光層とが陽極側から順に形
成された有機２層素子構造、或いは陽極と陰極との間に
有機発光層が形成された有機単層素子構造を有する電界
発光素子において、前記有機発光層が、下記一般式
〔Ｉ〕（化１）で表わされるオキサジアゾール系化合物
を構成成分とする層であることを特徴とする電界発光素
子が提供される。According to the present invention, there is provided an electroluminescent device comprising an anode and a cathode and one or a plurality of organic compound layers sandwiched therebetween.
At least one of the organic compound layers is a layer containing an oxadiazole compound represented by the following general formula [I] (Formula 1) as a constituent component. In addition, an organic three-layer element structure in which an organic hole transport layer, an organic light emitting layer, and an organic electron transport layer are sequentially formed from the anode side between the anode and the cathode, or an organic three-layer device structure is provided between the anode and the cathode. In an electroluminescent device having an organic two-layer device structure in which a light emitting layer and an organic electron transport layer are sequentially formed from the anode side, the organic electron transport layer has the following general formula [I].
There is provided an electroluminescent device comprising an oxadiazole-based compound represented by Chemical formula 1 as a constituent component. Further, between the anode and the cathode, an organic hole transport layer,
An organic three-layer element structure in which an organic light emitting layer and an organic electron transport layer are sequentially formed from the anode side, or between an anode and a cathode,
In an electroluminescent device having an organic two-layer device structure in which an organic hole transport layer and an organic light emitting layer are sequentially formed from the anode side, or an organic single layer device structure in which an organic light emitting layer is formed between an anode and a cathode. The organic light emitting layer is a layer containing an oxadiazole compound represented by the following general formula [I] (Formula 1) as a constituent component.
【化１】 [Chemical 1]
【０００８】本発明者らは、上記課題を解決するための
発光層の構成要素について鋭意検討した結果、陽極およ
び陰極と、これらの間に狭持された一層またはは複数層
の有機化合物層より構成される電界発光素子において、
前記有機化合物層のうち少なくとも一層が、前記一般式
〔Ｉ〕（化１）で表わされるオキサジアゾール系化合物
を構成成分とする層である電界発光素子が、上記課題に
対し、有効であることを見い出し、本発明を完成するに
至った。The inventors of the present invention have earnestly studied the constituent elements of the light emitting layer for solving the above-mentioned problems, and as a result, the anode and the cathode and one or a plurality of organic compound layers sandwiched between them are used. In the constructed electroluminescent device,
An electroluminescent device in which at least one of the organic compound layers is a layer containing an oxadiazole compound represented by the general formula [I] (Formula 1) as a constituent is effective for the above problems. The present invention has been completed and the present invention has been completed.
【０００９】本発明は前記したように有機化合物層の少
なくとも一層にオキサジアゾール系化合物を含有させた
ものであるが、かかる前記一般式〔Ｉ〕（化１）で表わ
されるオキサジアゾール系化合物のＡｒとしては、次の
ものが挙げられる。まず、Ａｒがアルキル基の場合、該
アルキル基としては、炭素数１〜６、好ましくは炭素数
１〜４の直鎖又は分岐鎖のアルキル基が挙げられる。更
にＡｒがアリール基、複素環式芳香環の場合、フェニ
ル、ナフチル、アントリル、アセナフテニル、フルオレ
ニル、フェナントリル、スチリル、ピリジル、ピリミジ
ル、フラニル、ピロリル、チオフェニル、キノリル、ベ
ンゾフラニル、ベンゾチオフェニル、インドリル、カル
バゾリル、ベンゾオキサゾリル、キノキサリル等が挙げ
られる。As described above, the present invention is one in which at least one layer of the organic compound layer contains an oxadiazole-based compound, and the oxadiazole-based compound represented by the general formula [I] Examples of Ar include the following. First, when Ar is an alkyl group, the alkyl group may be a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Further, when Ar is an aryl group or a heterocyclic aromatic ring, phenyl, naphthyl, anthryl, acenaphthenyl, fluorenyl, phenanthryl, styryl, pyridyl, pyrimidyl, furanyl, pyrrolyl, thiophenyl, quinolyl, benzofuranyl, benzothiophenyl, indolyl, carbazolyl, Examples thereof include benzoxazolyl and quinoxalyl.
【００１０】前記一般式〔Ｉ〕（化１）におけるＡｒの
置換基としては具体的には次のような基を挙げることが
できる。Specific examples of the substituent of Ar in the above general formula [I] (Formula 1) include the following groups.
【００１１】（１）ハロゲン原子、水酸基、トリフルオ
ロメチル基、シアノ基、ニトロ基。 （２）アルキル基；好ましくはＣ1〜Ｃ6とりわけＣ1〜
Ｃ4の直鎖または分岐鎖のアルキル基である。 （３）アリール基；炭素環式あるいは複素環式芳香環で
あり、フェニル、ナフチル、アントリル、アセナフテニ
ル、フルオレニル、フェナントリル、インデニル、ピレ
ニル、ピリジル、ピリミジル、フラニル、ピロニル、チ
オフェニル、キノリル、ベンゾフラニル、ベンゾチオフ
ェニル、インドリル、カルバゾリル、ベンゾオキサゾリ
ル、キノキサリル、ベンゾイミダゾリル、ピラゾリル、
ジベンゾフラニル、ジベンジチオフェニル等を示し、こ
れらのアリール基は更にハロゲン原子、水酸基、シアノ
基、ニトロ基、アルキル基、アルコキシ基、アミノ基等
で置換されていてもよい。 （４）アルコキシ基（−ＯＲ1）：Ｒ1は（２）で定義し
たアルキル基を表わす。 （５）アリールオキシ基；アリール基として（３）で定
義した基を示す。 （６）アルキルチオ基（−ＳＲ2）：Ｒ2は（２）で定義
した基を示す。 ルキル基、アセチル基、ベンゾイル基等のアシル基、ま
たは（３）で定義したアリール基を表わし、またピペリ
ジル基、モルホリル基のように、Ｒ3とＲ4が窒素原子と
共同で環を形成しても良い。またユロリジル基のように
アリール基上の炭素原子と共同で環を形成しても良い。 （８）アルコキシカルボニル基（−ＣＯＯＲ5）：Ｒ5は
（２）で定義したアルキル基、または（３）で定義した
アリール基を表わす。 （９）アシル基（−ＣＯＲ5）、スルホニル基（−ＳＯ2
Ｒ5）、カルバモイル基 及びＲ5は上記で定義した意味を表わす。但しＲ3及びＲ
4においてアリール基上の炭素原子と共同で環を形成す
る場合を除く。 （１０）メチレンジオキシ基またはメチレンジチオ基等
のアルキレンジオキシ基またはアルキレンジチオ基。 （１１）スチリル基（−ＣＨ＝ＣＨ−Ｃ6Ｈ4−Ｒ5） Ｒ5は（１）〜（１０）で定義した置換基を表わす。(1) Halogen atom, hydroxyl group, trifluor
Romethyl group, cyano group, nitro group. (2) Alkyl group; preferably C1~ C6Especially C1~
CFourIs a linear or branched alkyl group. (3) Aryl group; carbocyclic or heterocyclic aromatic ring
Yes, phenyl, naphthyl, anthryl, acenaphthenic
Le, fluorenyl, phenanthryl, indenyl, pyret
Nyl, pyridyl, pyrimidyl, furanyl, pyronyl, thiyl
Ophenyl, quinolyl, benzofuranyl, benzothiof
Phenyl, indolyl, carbazolyl, benzoxazoli
, Quinoxalyl, benzimidazolyl, pyrazolyl,
Dibenzofuranyl, dibenzdithiophenyl, etc.
These aryl groups also include halogen atoms, hydroxyl groups, and cyano groups.
Group, nitro group, alkyl group, alkoxy group, amino group, etc.
May be replaced with. (4) Alkoxy group (-OR1): R1Is defined in (2)
Represents an alkyl group. (5) Aryloxy group; defined as the aryl group in (3)
The defined group is shown. (6) Alkylthio group (-SR2): R2Is defined in (2)
The group represented by Acyl group such as alkyl group, acetyl group, benzoyl group,
Or represents an aryl group as defined in (3),
R such as a dil group and a morpholyl group3And RFourIs a nitrogen atom
You may form a ring jointly. Also like the urolysyl group
It may form a ring in cooperation with the carbon atom on the aryl group. (8) Alkoxycarbonyl group (-COORFive): RFiveIs
Alkyl group defined in (2) or defined in (3)
Represents an aryl group. (9) Acyl group (-CORFive), A sulfonyl group (-SO2
RFive), Carbamoyl group And RFiveRepresents the meaning defined above. However, R3And R
FourForm a ring with a carbon atom on the aryl group in
Except when (10) Methylenedioxy group or methylenedithio group, etc.
An alkylenedioxy group or an alkylenedithio group. (11) Styryl group (-CH = CH-C6HFour-RFive) RFiveRepresents a substituent defined in (1) to (10).
【００１２】次に本発明で使用される前記一般式〔Ｉ〕
（化１）で表わされるオキサジアゾール系化合物の具体
例を表１に示すが、本発明はこれらに限定されるもので
はない。Next, the above-mentioned general formula [I] used in the present invention is used.
Specific examples of the oxadiazole-based compound represented by (Chemical Formula 1) are shown in Table 1, but the present invention is not limited thereto.
【００１３】[0013]
【表１】 [Table 1]
【００１４】本発明における電界発光素子は以上で説明
した化合物を真空蒸着法、溶液塗布法等により薄膜化
し、陽極及び陰極で狭持することにより構成される。そ
の際、化合物中に添加物として他の物質を複数種添加す
ることもできる。また、電極からの電荷注入効率を向上
させるために電極注入輸送層を電極との間に別に設ける
ことも可能である。The electroluminescent device of the present invention is formed by thinning the compound described above by a vacuum vapor deposition method, a solution coating method or the like, and sandwiching it by an anode and a cathode. At that time, plural kinds of other substances may be added to the compound as additives. Further, an electrode injecting and transporting layer may be separately provided between the electrode and the electrode in order to improve the efficiency of injecting charge from the electrode.
【００１５】陽極材料としてはニッケル、金、白金、パ
ラジウムやこれらの合金或いは酸化錫（ＳｎＯ2）、酸
化錫インジウム（ＩＴＯ）、沃化銅などの仕事関数の大
きな金属やそれらの合金、化合物、更にはポリ（３−メ
チルチオフェン）、ポリピロール等の導電性ポリマーな
どを用いることができる。As the anode material, nickel, gold, platinum, palladium and alloys thereof, or metals having a large work function such as tin oxide (SnO 2 ), indium tin oxide (ITO) and copper iodide, alloys and compounds thereof, Further, conductive polymers such as poly (3-methylthiophene) and polypyrrole can be used.
【００１６】一方、陰極材料としては、仕事関数の小さ
な銀、錫、鉛、マグネシウム、マンガン、アルミニウ
ム、或いはこれらの合金が用いられる。陽極及び陰極と
して用いる材料のうち少なくとも一方は、素子の発光波
長領域において充分透明であることが望ましい。具体的
には８０％以上の光透過率を有することが望ましい。On the other hand, as the cathode material, silver, tin, lead, magnesium, manganese, aluminum, or an alloy thereof having a small work function is used. At least one of the materials used as the anode and the cathode is preferably sufficiently transparent in the emission wavelength region of the device. Specifically, it is desirable to have a light transmittance of 80% or more.
【００１７】図１〜４に本発明に係る電界発光素子の代
表的な構成例を示す。図１において、１は基板、２，４
は電極、３ａは発光層、３ｂは電子輸送層、３ｃは正孔
輸送層である。図１は、基板１上に電極２を設け、電極
２上に発光層３ａを単独で設け、その上に電極を設けた
構成のものである。図２は、図１において電極２と発光
層３ａの間に正孔輸送層３ｃを設けたものであり、図３
は、図１において発光層３ａと電極４の間に電子輸送層
３ｂを設けたものである。図４は、図３において電極２
と発光層３ａとの間に正孔輸送層３ｃを設けた構成のも
のである。1 to 4 show typical constitutional examples of the electroluminescent device according to the present invention. In FIG. 1, 1 is a substrate and 2, 4
Is an electrode, 3a is a light emitting layer, 3b is an electron transport layer, and 3c is a hole transport layer. FIG. 1 shows a structure in which an electrode 2 is provided on a substrate 1, a light emitting layer 3a is independently provided on the electrode 2, and an electrode is provided thereon. 2 shows a structure in which the hole transport layer 3c is provided between the electrode 2 and the light emitting layer 3a in FIG.
In FIG. 1, an electron transport layer 3b is provided between the light emitting layer 3a and the electrode 4 in FIG. FIG. 4 shows the electrode 2 in FIG.
The hole transport layer 3c is provided between the light emitting layer 3a and the light emitting layer 3a.
【００１８】本発明の電界発光素子は以上の各層をガラ
ス等の透明基板上に順次積層されて素子として構成され
るわけであるが、素子の安定性の向上、特に大気中の水
分に対する保護のために、別に保護層を設けたり、素子
全体をセル中に入れ、シリコンオイル等を封入するよう
にしてもよい。The electroluminescent device of the present invention is constructed as a device by sequentially laminating the above-mentioned layers on a transparent substrate such as glass. However, the stability of the device is improved, and in particular, protection against moisture in the atmosphere is provided. Therefore, a protective layer may be separately provided, or the entire device may be put in a cell and silicon oil or the like may be sealed therein.
【００１９】以下、実施例により本発明を更に詳細に説
明する。 実施例１ ガラス基板上に大きさ３ｍｍ×３ｍｍ、厚さ７００Åの
酸化錫インジウム（ＩＴＯ）による陽極を形成し、その
上に下記構造式（化２）で表わされるジアミン誘導体か
らなるホール輸送層５００Å、前記表１中のＮｏ．１２
の化合物からなる電子輸送層５００Å、アルミニウムか
らなる陰極を各々真空蒸着により形成し、電界発光素子
を作製した。蒸着時の真空度は約０．７×１０-6ｔｏｒ
ｒであり、基板温度は室温である。このようにして作製
した素子の陽極及び陰極にリード線介して直流電源を接
続したところ電流密度５０ｍＡ／ｃｍ2において印加電
圧が２５Ｖであり、白色の明瞭な発光が長時間にわたっ
て確認された。この時の発光波長は５３７ｎｍと４０７
ｎｍにピークを有し、輝度は４００ｃｄ／ｍ2であっ
た。Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 An anode made of indium tin oxide (ITO) having a size of 3 mm × 3 mm and a thickness of 700 Å was formed on a glass substrate, and a hole transport layer 500 Å made of a diamine derivative represented by the following structural formula (Formula 2) was formed thereon. No. in Table 1 above. 12
An electron-transporting layer 500Å made of the above compound and a cathode made of aluminum were respectively formed by vacuum vapor deposition to produce an electroluminescent device. The degree of vacuum during vapor deposition is approximately 0.7 × 10 -6 torr.
r, and the substrate temperature is room temperature. When a direct current power supply was connected to the anode and cathode of the device thus produced through a lead wire, the applied voltage was 25 V at a current density of 50 mA / cm 2 , and clear white light emission was confirmed for a long time. The emission wavelengths at this time are 537 nm and 407
It had a peak at nm and a luminance of 400 cd / m 2 .
【化２】 なお、この素子は１ヵ月保存後においても明瞭な発光が
認められた。[Chemical 2] It should be noted that this device showed clear light emission even after storage for 1 month.
【００２０】実施例２ ホール輸送性発光層として下記構造式（化３）で表わさ
れる化合物を用いた以外は実施例１と同様にして電界発
光素子を作製した。このようにして作製した素子の陽極
及び陰極にリード線介して直流電源を接続したところ電
流密度１０ｍＡ／ｃｍ2において印加電圧が２８Ｖであ
り、青色の明瞭な発光が長時間にわたって確認された。
この時の発光波長は４６４ｎｍで輝度は４０ｃｄ／ｍ2
であった。尚、この例では前記表１中のＮｏ．１２の化
合物よりなる層は、電子輸送層として機能したことが理
解される。Example 2 An electroluminescent device was produced in the same manner as in Example 1 except that the compound represented by the following structural formula (Formula 3) was used as the hole transporting light emitting layer. When a direct current power supply was connected to the anode and cathode of the device thus produced via a lead wire, the applied voltage was 28 V at a current density of 10 mA / cm 2 , and clear blue light emission was confirmed for a long time.
At this time, the emission wavelength is 464 nm and the brightness is 40 cd / m 2.
Met. In this example, No. 1 in Table 1 above is used. It is understood that the layer composed of 12 compounds functioned as an electron transport layer.
【化３】 [Chemical 3]
【００２１】実施例３ ホール輸送性発光層として下記構造式（化４）で表わさ
れる化合物を５００Å、電子輸送層として前記表１中の
Ｎｏ．１２の化合物を５００Å、陰極としてＭｇＡｇ
（１０：１）を２０００Å、それぞれ真空蒸着により形
成し、素子を作製した。このようにして作製した素子に
直流電圧を印加したところ、印加電圧１２．５Ｖ、電流
密度１００ｍＡ／ｃｍ2において、２０００ｃｄ／ｍ2の
発光輝度が観測された。この時発光波長は５１０ｎｍで
あった。Example 3 A compound represented by the following structural formula (Formula 4) was used as a hole-transporting light-emitting layer in an amount of 500 L, and an electron-transporting layer having No. 500 liters of 12 compounds, MgAg as cathode
2000Å of (10: 1) was formed by vacuum vapor deposition to fabricate a device. When a direct current voltage was applied to the element thus manufactured, an emission luminance of 2000 cd / m 2 was observed at an applied voltage of 12.5 V and a current density of 100 mA / cm 2 . At this time, the emission wavelength was 510 nm.
【化４】 [Chemical 4]
【００２２】実施例４ 実施例３と同様にして、Ｅｌ素子を作製した。ただし、
ホール輸送性発光層として、下記構造式（化５）で表わ
される化合物を用いた。このようにして作製したＥｌ素
子に直流電圧を印加したところ、印加電圧９Ｖ．、電流
密度３０ｍＡ／ｃｍ2において、８ｃｄ／ｍ2の発光輝度
が観測された。また、この素子を３０ｍＡ／ｃｍ2の定
電流下で駆動したところ、１時間後において、駆動電
圧、２４Ｖ、発光輝度２１５ｃｄ／ｍ2が観測され、経
時と共に、発光効率の増加が認められた。Example 4 An El element was manufactured in the same manner as in Example 3. However,
As the hole-transporting light emitting layer, a compound represented by the following structural formula (Formula 5) was used. When a DC voltage was applied to the El element thus manufactured, the applied voltage was 9V. At a current density of 30 mA / cm 2 , an emission luminance of 8 cd / m 2 was observed. When this device was driven under a constant current of 30 mA / cm 2 , after 1 hour, a driving voltage, 24 V, and a light emission luminance of 215 cd / m 2 were observed, and it was confirmed that the light emission efficiency increased with time.
【化５】 [Chemical 5]
【００２３】実施例５ 実施例１と同様のＩＴＯ基板にホール輸送層として下記
構造式化６で表される化合物を４００Å、発光層として
下記構造式化７で表される化合物を１５０Å、さらに電
子輸送層として前記化合物Ｎｏ．１２の化合物を５００
Å蒸着し、ＥＬ素子を作製した。この様にして得られた
ＥＬ素子に直流電圧を印加し駆動したところ、駆動電圧
６．４Ｖ、電流密度３０ｍＡ／ｃｍ2において、６４０
ｃｄ／ｍ2の発光輝度を示し、発光ピーク波長は４７５
ｎｍであり、発光層に基づくＥＬ発光が観測された。こ
のＥＬ素子を電流密度３０ｍＡ／ｃｍ2の定電流下で駆
動したところ、１時間おいても３００ｃｄ／ｍ2の輝度
を維持していた。Example 5 On the same ITO substrate as in Example 1, 400 Å of the compound represented by the following structural formula 6 was used as a hole transport layer, and 150 Å of the compound represented by the following structural formula 7 was used as a light emitting layer, and further, an electron was used. As the transport layer, the compound No. 500 compounds of 12 compounds
Å Vapor deposition was performed to fabricate an EL device. When a direct current voltage was applied to the EL device thus obtained and the device was driven, 640 at a driving voltage of 6.4 V and a current density of 30 mA / cm 2 .
The emission brightness is cd / m 2 , and the emission peak wavelength is 475.
nm, and EL emission based on the light emitting layer was observed. When this EL device was driven under a constant current with a current density of 30 mA / cm 2 , the brightness of 300 cd / m 2 was maintained even after 1 hour.
【化６】 [Chemical 6]
【化７】 [Chemical 7]
【００２４】実施例６〜１６ 発光層を構成する化合物を下記表３で表される化合物に
代えた以外は実施例５と同様にしてＥＬ素子を作製し
た。この様にして作製したＥＬ素子に直流電圧を印加し
て駆動したところ表４に記した素子特性を示した。Examples 6 to 16 EL devices were prepared in the same manner as in Example 5 except that the compounds constituting the light emitting layer were replaced with the compounds shown in Table 3 below. When the EL device thus manufactured was driven by applying a DC voltage, the device characteristics shown in Table 4 were exhibited.
【００２５】実施例１７〜２４ 電子輸送層を構成する化合物を下記表５で表される化合
物に代えた以外は実施例５と同様にしてＥＬ素子を作製
した。この様にして作製したＥＬ素子に直流電圧を印加
して駆動したところ表５に記した素子特性を示した。Examples 17 to 24 EL devices were prepared in the same manner as in Example 5 except that the compounds shown in Table 5 below were used instead of the compounds constituting the electron transport layer. When the EL device thus manufactured was driven by applying a DC voltage, the device characteristics shown in Table 5 were exhibited.
【００２６】[0026]
【表３】 [Table 3]
【００２７】[0027]
【表４】 [Table 4]
【００２８】[0028]
【表５】 [Table 5]
【００２９】比較例 実施例１において、電子輸送層に用いた前記表１中のＮ
ｏ．１２の化合物の代りに、下記構造式（化６）で表わ
される化合物を用いた以外は、実施例１と同様にして電
界発光素子を作成した。Comparative Example In Example 1, the N in Table 1 used for the electron transport layer was used.
o. An electroluminescent device was produced in the same manner as in Example 1 except that the compound represented by the following structural formula (Formula 6) was used in place of the compound of 12.
【化６】 この素子を同様に発光させたところ緑色の発光が認めら
れた。この素子を１ヶ月室温に保存後においては発光は
認められなかった。[Chemical 6] When this device was similarly made to emit light, green light emission was observed. No light emission was observed after the device was stored at room temperature for 1 month.
【００３０】[0030]
【発明の効果】本発明の電界発光素子は、有機化合物の
構成材料として前記一般式〔Ｉ〕（化１）で表わされる
オキサジアゾール系化合物を用いたことから、発光性能
が長期間にわたって持続し、耐久性に優れたものであ
る。In the electroluminescent device of the present invention, since the oxadiazole compound represented by the general formula [I] (Formula 1) is used as the constituent material of the organic compound, the luminous performance is sustained for a long period of time. However, it has excellent durability.
【図１】本発明に係る電界発光素子の模式断面図であ
る。FIG. 1 is a schematic cross-sectional view of an electroluminescent device according to the present invention.
【図２】本発明に係る他の電界発光素子の模式断面図で
ある。FIG. 2 is a schematic cross-sectional view of another electroluminescent device according to the present invention.
【図３】本発明に係る別の電界発光素子の模式断面図で
ある。FIG. 3 is a schematic cross-sectional view of another electroluminescent device according to the present invention.
【図４】本発明に係る更に別の電界発光素費の模式断面
図である。FIG. 4 is a schematic cross-sectional view of yet another electroluminescent element according to the present invention.
１…基板 ２，４…電極 ３ａ…発光層 ３ｂ…電子輸送層 ３ｃ…正孔輸送層 DESCRIPTION OF SYMBOLS 1 ... Substrate 2, 4 ... Electrode 3a ... Light emitting layer 3b ... Electron transport layer 3c ... Hole transport layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安達 千波矢 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 (72)発明者 高橋 俊彦 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chihaya Adachi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Toshihiko Takahashi 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh
Claims (3)
れた一層または複数層の有機化合物層より構成される電
界発光素子において、前記有機化合物層のうち少なくと
も一層が、下記一般式〔Ｉ〕（化１）で表わされるオキ
サジアゾール系化合物を構成成分とする層であることを
特徴とする電界発光素子。 【化１】 1. An electroluminescent device comprising an anode and a cathode, and one or a plurality of organic compound layers sandwiched therebetween, wherein at least one of the organic compound layers has the following general formula [I ] An electroluminescent device comprising a layer containing an oxadiazole-based compound represented by Chemical formula 1 as a constituent component. [Chemical 1]
と、有機発光層と、有機電子輸送層とが陽極側から順に
形成された有機３層素子構造、或いは陽極と陰極との間
に、有機発光層と、有機電子輸送層とが陽極側から順に
形成された有機２層素子構造を有する電界発光素子にお
いて、 前記有機電子輸送層が、請求項１に記載の一般式〔Ｉ〕
（化１）で示されるオキサジアゾール系化合物を構成成
分とする層であることを特徴とする電界発光素子。2. An organic three-layer device structure in which an organic hole transport layer, an organic light emitting layer, and an organic electron transport layer are sequentially formed from the anode side between the anode and the cathode, or between the anode and the cathode. In the electroluminescent device having the organic two-layer device structure in which the organic light emitting layer and the organic electron transporting layer are sequentially formed from the anode side, the organic electron transporting layer is the general formula [I] according to claim 1.
An electroluminescent device comprising a layer containing an oxadiazole-based compound represented by (Chemical Formula 1) as a constituent component.
と、有機発光層と、有機電子輸送層とが陽極側から順に
形成された有機３層素子構造、或いは陽極と陰極との間
に、有機ホール輸送層と、有機発光層とが陽極側から順
に形成された有機２層素子構造、或いは陽極と陰極との
間に有機発光層が形成された有機単層素子構造を有する
電界発光素子において、 前記有機発光層が、請求項１に記載の一般式〔Ｉ〕（化
１）で表わされるオキサジアゾール系化合物を構成成分
とする層であることを特徴とする電界発光素子。3. An organic three-layer device structure in which an organic hole transport layer, an organic light emitting layer, and an organic electron transport layer are sequentially formed from the anode side between the anode and the cathode, or between the anode and the cathode. In addition, an electroluminescence having an organic two-layer element structure in which an organic hole transport layer and an organic light emitting layer are sequentially formed from the anode side, or an organic single layer element structure in which an organic light emitting layer is formed between an anode and a cathode. In the device, the organic light-emitting layer is a layer containing an oxadiazole compound represented by the general formula [I] (Formula 1) as a constituent component according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5104993A JPH0665569A (en) | 1992-06-20 | 1993-04-07 | Electroluminescent element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-186051 | 1992-06-20 | ||
| JP18605192 | 1992-06-20 | ||
| JP5104993A JPH0665569A (en) | 1992-06-20 | 1993-04-07 | Electroluminescent element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0665569A true JPH0665569A (en) | 1994-03-08 |
Family
ID=26445352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5104993A Pending JPH0665569A (en) | 1992-06-20 | 1993-04-07 | Electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665569A (en) |
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| US11393997B2 (en) | 2012-04-13 | 2022-07-19 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, electronic device, and lighting device |
| US9065066B2 (en) | 2012-04-13 | 2015-06-23 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, electronic device, and lighting device |
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