JPH06240245A - Electroluminescent element - Google Patents
Electroluminescent elementInfo
- Publication number
- JPH06240245A JPH06240245A JP5051545A JP5154593A JPH06240245A JP H06240245 A JPH06240245 A JP H06240245A JP 5051545 A JP5051545 A JP 5051545A JP 5154593 A JP5154593 A JP 5154593A JP H06240245 A JPH06240245 A JP H06240245A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- layers
- electroluminescent device
- anode
- cathode
- 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
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 125
- 150000002894 organic compounds Chemical class 0.000 claims description 26
- 239000000470 constituent Substances 0.000 claims description 23
- 230000005525 hole transport Effects 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 9
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 3
- 230000005923 long-lasting effect Effects 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 16
- -1 aromatic tertiary amines Chemical class 0.000 description 15
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- TXSXFUNPJLCBOV-UHFFFAOYSA-N 1-phenylpyren-2-amine Chemical compound NC1=C(C2=CC=C3C=CC=C4C=CC(=C1)C2=C43)C4=CC=CC=C4 TXSXFUNPJLCBOV-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 150000004866 oxadiazoles Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 2
- YZVWKHVRBDQPMQ-UHFFFAOYSA-N 1-aminopyrene Chemical class C1=C2C(N)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 YZVWKHVRBDQPMQ-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 150000001893 coumarin derivatives Chemical class 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 150000007978 oxazole derivatives Chemical class 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000005530 alkylenedioxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 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
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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、低消費電力発光
体、微小体積発光体、軽量発光体あるいは大面積の面状
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, and can be used as a conventional incandescent lamp, fluorescent lamp or light emitting diode. In contrast, the present invention relates to an electroluminescent device that enables realization of a low power consumption light emitter, a micro volume light emitter, a light weight light emitter, or a large-area planar light emitter.
【０００２】[0002]
【従来の技術】近年、情報機器の多様化及び省スペース
化に伴い、ＣＲＴよりも低消費電力で空間占有面積の少
ない平面表示素子へのニーズが高まっている。このよう
な平面表示素子としては、液晶、プラズマディスプレイ
などがあるが、特に最近は自己発光型で表示が鮮明な、
また直流定電圧駆動が可能な有機電界発光素子への期待
が高まっている。有機電界発光素子の素子構造として
は、これまで２層構造（ホール注入電極と電子注入電極
の間に、ホール輸送層と発光層が形成された構造（ＳＨ
−Ａ構造）（特開昭５９−１９４３９３号，Ａｐｐｌ．
Ｐｈｙｓ．Ｌｅｔｔ．５１，９１３（１９８７）、また
は、ホール注入電極と電子注入電極の間に発光層と電子
輸送層とが形成された構造（ＳＨ−Ｂ構造）（ＵＳＰ
Ｎｏ．５，０８５９４７、特開平２−２５０９２号，Ａ
ｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．５５，１４８９（１９８
９））、あるいは３層構造（ホール注入電極と電子注入
電極との間にホール輸送層と発光層と電子輸送層とが形
成された構造（ＤＨ構造）（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅ
ｔｔ．５７，５３１（１９９０））の素子構造が報告さ
れている。2. Description of the Related Art In recent years, with the diversification and space saving of information equipment, there is an increasing need for a flat display device which consumes less power and occupies less space than a CRT. Liquid crystal, plasma displays, etc. are available as such flat display elements. Recently, in particular, self-emission type displays have a clear display.
In addition, there are increasing expectations for organic electroluminescent devices that can be driven with a constant DC voltage. A device structure of an organic electroluminescent device has so far been a two-layer structure (a structure in which a hole transport layer and a light emitting layer are formed between a hole injection electrode and an electron injection electrode (SH
-A structure) (JP-A-59-194393, Appl.
Phys. Lett. 51, 913 (1987), or a structure in which a light emitting layer and an electron transport layer are formed between a hole injecting electrode and an electron injecting electrode (SH-B structure) (USP).
No. 5,085947, JP-A-2-25092, A
ppl. Phys. Lett. 55, 1489 (198
9)) or a three-layer structure (a structure in which a hole transport layer, a light emitting layer, and an electron transport layer are formed between a hole injection electrode and an electron injection electrode (DH structure) (Appl.Phys.Le).
tt. 57, 531 (1990)) has been reported.
【０００３】上記ホール注入電極としては、ＡｕやＩＴ
Ｏ（酸化錫インジウム）などの様な仕事関数の大きな電
極材料を用い、電子注入電極としては、Ｃａ、Ｍｇ、Ａ
ｌ等及びそれらの合金等の仕事関数の小さな電極材料を
用いる。また、現在まで、上記ホール輸送層、発光層、
電子輸送層に使用可能な材料として様々な有機化合物が
報告されている。これらに使用される有機材料として
は、例えば、ホール輸送層としては芳香族第３級アミン
が、発光層材料としてはアルミニウムトリスオキシン
（特開昭５９−１９４３９３，特開昭６３−２９５６９
５）、スチリルアミン誘導体、スチリルベンゼン誘導体
等（特開平２−２０９９８８）が、また、電子輸送層と
しては、オキサジアゾール誘導体等（日本化学会誌Ｎ
ｏ．１１，ｐ１５４０（１９９１）が報告されている。
現在まで、様々な素子構造及び有機材料を用いることに
より、初期的には１０００ｃｄ／ｍ2以上の高輝度発
光、駆動電圧１０Ｖ程度の素子が得られているが、連続
駆動を行った場合、従来の有機材料では数時間で光出力
の低下、駆動電圧の上昇が観測され、ＥＬ素子の長期耐
久性には大きな問題を抱えている。特に青色発光素子に
おいては、まだ材料の探索が十分に行われておらず、発
光効率の向上など多くの課題が残されている。これらの
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開発の歴史も浅く、未だその材料研
究やデバイス化への研究が十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
が実状である。As the hole injecting electrode, Au or IT is used.
An electrode material having a large work function such as O (indium tin oxide) is used, and Ca, Mg, A is used as the electron injection electrode.
Electrode materials having a low work function such as 1 and the like and alloys thereof are used. Until now, the hole transport layer, the light emitting layer,
Various organic compounds have been reported as materials that can be used for the electron transport layer. Examples of organic materials used for these are aromatic tertiary amines for the hole transport layer, and aluminum trisoxine for the light emitting layer material (JP-A-59-194393, JP-A-63-29569).
5), styrylamine derivatives, styrylbenzene derivatives and the like (JP-A-2-209988), and as the electron transport layer, oxadiazole derivatives and the like (Journal of the Chemical Society of Japan N
o. 11, p1540 (1991) has been reported.
Up to now, by using various element structures and organic materials, an element with high-luminance light emission of 1000 cd / m 2 or more and a driving voltage of about 10 V has been obtained initially. In the organic material, a decrease in light output and an increase in driving voltage are observed in a few hours, and there is a big problem in the long-term durability of the EL element. Particularly in blue light emitting devices, the search for materials has not been sufficiently conducted, and many problems such as improvement in light emission efficiency remain. Carrier injection type electroluminescent devices using organic compounds as light emitters, including these examples, have a short history of research and development, and it cannot be said that the material research and device research have been sufficiently conducted. The reality is that there are many problems such as further improvement of brightness, control of emission wavelength, and improvement of durability.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記従来技
術の実情に鑑みて成されたものであり、その目的は十分
な輝度と発光性能が長時間に亘って持続する耐久性に優
れた有機電界発光素子（有機ＥＬ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 above-mentioned conventional circumstances, and an object thereof is to have sufficient luminance and excellent durability for long-term emission performance. It is to provide an organic electroluminescence device (organic EL device).
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するための有機ＥＬ素子の構成要素について鋭意
検討した結果、陽極及び陰極と、これらの間に挟持され
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
発光層素子において、前記有機化合物層のうち少なくと
も一層を、特定なアミノフェニルピレンを構成成分とす
る層とすることにより、上記課題に対し有効な電界発光
素子を提供できることを見いだした。Means for Solving the Problems The inventors of the present invention have made earnest studies on the constituent elements of an organic EL device for solving the above problems, and as a result, have formed an anode and a cathode and one or more layers sandwiched between them. In the electroluminescent layer element constituted by the organic compound layer, the electroluminescent element effective for the above problems is obtained by forming at least one of the organic compound layers as a layer containing a specific aminophenylpyrene as a constituent component. I found what I could offer.
【０００６】また、陽極及び陰極の間に、一層以上の正
孔輸送層及び一層以上の発光層を構成要素として含有す
る電界発光素子あるいは、陽極及び陰極の間に、一層以
上の正孔輸送層及び一層以上の発光層及び一層以上の電
子輸送層を構成要穀として含有する電界発光素子におい
て、前記正孔輸送層のうち少なくとも一層を、特定なア
ミノフェニルピレンを構成成分とする層とすることによ
って更に有効な電界発光素子を提供できることを見いだ
した。Further, an electroluminescent device containing one or more hole transport layers and one or more light emitting layers as components between the anode and the cathode, or one or more hole transport layers between the anode and the cathode. And in an electroluminescent device containing one or more light-emitting layers and one or more electron-transporting layers as constituent grains, at least one of the hole-transporting layers is a layer containing a specific aminophenylpyrene as a constituent component. It has been found that an even more effective electroluminescent device can be provided.
【０００７】更に、陽極及び陰極の間に、一層以上の発
光層及び一層以上の電子輸送層を構成要素として含有す
る電界発光素子、あるいは陽極及び陰極の間に、一層以
上の正孔輸送層及び一層以上の発光層及び一層以上の電
子輸送層を構成要素として含有する電界発光素子、ある
いは陽極及び陰極の間に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、前記発光層のう
ち少なくとも一層を、特定なアミノフェニルピレンを構
成成分とする層とすることによっても同様に有効な電界
発光素子を提供できることを見いだした。Further, between the anode and the cathode, an electroluminescent device containing one or more light emitting layers and one or more electron transport layers as constituent elements, or between the anode and the cathode, one or more hole transport layers and An electroluminescent device comprising one or more light emitting layers and one or more electron transport layers as constituent elements, or an electroluminescent device having an organic single layer device structure in which a light emitting layer is formed between an anode and a cathode, wherein It has been found that a similarly effective electroluminescent device can be provided by forming at least one of the layers containing a specific aminophenylpyrene as a constituent component.
【０００８】すなわち、本発明によれば、陽極及び陰極
と、これらの間に挟持された一層または複数層の有機化
合物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、下記一般式化１で表さ
れる有機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。That is, according to the present invention, in an electroluminescent device composed of an anode and a cathode and one or a plurality of layers of an organic compound sandwiched therebetween, at least one of the organic compound layers is There is provided an electroluminescent device comprising a layer containing an organic compound represented by the general formula 1 as a constituent component.
【化１】 （式中、Ａｒ1、Ａｒ2は置換もしくは無置換のアルキル
基、置換もしくは無置換のアリール基又は置換もしくは
無置換の複素環式芳香環を表す。）また、本発明によれ
ば、陽極及び陰極の間に、一層以上の正孔輸送層及び一
層以上の発光層を構成要素として含有する電界発光素子
あるいは、陽極及び陰極の間に、一層以上の正孔輸送層
及び一層以上の発光層及び一層以上の電子輸送層を構成
要素として含有する電界発光素子において、前記正孔輸
送層のうち少なくとも一層が、上記一般式（Ｉ）（化
１）で表される有機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、更には、陽極
及び陰極の間に、一層以上の発光層及び一層以上の電子
輸送層を構成要素として含有する電界発光素子、あるい
は陽極及び陰極の間に、一層以上の正孔輸送層及び一層
以上の発光層及び一層以上の電子輸送層を構成要素とし
て含有する電界発光素子、あるいは陽極及び陰極の間に
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、前記発光層のうち少なくとも一層が、上
記一般式（Ｉ）（化１）で表される有機化合物を構成成
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。[Chemical 1] (In the formula, Ar 1 and Ar 2 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic aromatic ring.) Further, according to the present invention, an anode and Between the cathode, an electroluminescent device containing one or more hole transport layers and one or more light emitting layers as constituent elements, or between the anode and the cathode, one or more hole transport layers and one or more light emitting layers, and In an electroluminescent device containing one or more electron-transporting layers as a constituent element, at least one of the hole-transporting layers is a layer containing an organic compound represented by the general formula (I) (Chemical Formula 1) as a constituent component. And an electroluminescent device comprising one or more light emitting layers and one or more electron transport layers as constituent elements between the anode and the cathode, or the anode and the cathode. of , An electroluminescent device containing one or more hole transport layers and one or more light emitting layers and one or more electron transport layers as constituent elements, or an organic single layer device structure in which a light emitting layer is formed between an anode and a cathode. In the electroluminescent device having: an electroluminescent device, wherein at least one of the light emitting layers is a layer containing an organic compound represented by the general formula (I) (Formula 1) as a constituent component. To be done.
【０００９】本発明は前記したように有機化合物層の少
なくとも一層に特定なアミノフェニルピレン化合物を含
有させたものであるが、かかる前記一般式（Ｉ）（化
１）で表される化合物について以下に具体例を挙げて説
明する。ただし、本発明はこれらに限定されるものでは
ない。The present invention includes a specific aminophenylpyrene compound contained in at least one layer of the organic compound layer as described above. Regarding the compound represented by the general formula (I) (Formula 1), A specific example will be described below. However, the present invention is not limited to these.
【００１０】前記一般式（Ｉ）においては、Ａｒ1、Ａ
ｒ2としては次のものが挙げられる。アリール基、複素
環式芳香環としては、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、ピレニル、フェナ
ントリル、スチリル、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。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。In the general formula (I), Ar 1 , A
Examples of r 2 include the following. Examples of the aryl group and the heterocyclic aromatic ring are phenyl, naphthyl, anthryl, acenaphthenyl, fluorenyl, pyrenyl, phenanthryl, styryl, pyrimidyl, furanyl, pyrrolyl, thiophenyl, quinolyl, benzofuranyl, benzothiophenyl, indolyl, carbazolyl, benzoxazoli. And quinoxalyl. Examples of the alkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
【００１１】前記一般式（Ｉ）におけるＡｒ1、Ａｒ2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。 （１）ハロゲン原子、水素原子、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、ジベンゾ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、アリール基、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−Ｃ6Ｈ5−Ｒ5） Ｒ5は（１）〜（１０）で定義した置換基又は水素原子
を表わす。 置換基又は水素原子を表わす。Ar in the general formula (I)1, Ar2of
Specific examples of the substituent include the following groups.
it can. (1) Halogen atom, hydrogen atom, trifluoromethyl
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, dibenzothiophenyl, etc.
These aryl groups also include halogen atoms, hydroxyl groups, and cyano groups.
Group, nitro group, alkyl group, aryl group, alkoxy
It may be substituted with a group, an amino group or the like. (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 groupAnd 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-C6HFive-RFive) RFiveIs a substituent or hydrogen atom defined in (1) to (10)
RepresentsRepresents a substituent or a hydrogen atom.
【００１２】次に、本発明で使用される前記一般式
（Ｉ）で表わされるアミノフェニルピレン系化合物の具
体例を以下に示す。Next, specific examples of the aminophenylpyrene compound represented by the general formula (I) used in the present invention are shown below.
【００１３】[0013]
【表１−（１）】 [Table 1- (1)]
【００１４】[0014]
【表１−（２）】 [Table 1- (2)]
【００１５】[0015]
【表１−（３）】 [Table 1- (3)]
【００１６】本発明における電界発光素子は、以上で説
明した有機化合物を真空蒸着法、溶液塗布法等により、
有機化合物層全体で０．５μｍより小さい厚み、さらに
好ましくは、各有機化合物層を１０ｎｍ〜１００ｎｍの
厚みに薄膜化することにより有機化合物層を形成し、陽
極及び陰極で直接または間接的に挟持することにより構
成される。また、構成有機化合物が著しく薄膜形成能に
富む場合、１０ｎｍ以下の膜厚において層を形成するこ
とも可能である。また、各有機化合物層中に添加物とし
て他の物質を複数種でも添加することもできる。The electroluminescent device according to the present invention is obtained by subjecting the above-described organic compound to a vacuum deposition method, a solution coating method, or the like.
The thickness of the entire organic compound layer is smaller than 0.5 μm, more preferably, the organic compound layer is formed by thinning each organic compound layer to a thickness of 10 nm to 100 nm, and the organic compound layer is directly or indirectly sandwiched between the anode and the cathode. It is composed of In addition, when the constituent organic compound is extremely rich in thin film forming ability, it is possible to form a layer with a film thickness of 10 nm or less. Also, a plurality of other substances may be added as an additive to each organic compound layer.
【００１７】本発明の電界発光素子は発光層に電気的に
バイアスを印加し発光させるものであるが、わずかなピ
ンホールによって短絡をおこし、素子として機能しなく
なる場合もあるので、有機化合物層の形成には皮膜形成
性に優れた化合物を併用することが望ましい。さらにこ
のような皮膜形成性に優れた化合物とポリマー結合剤を
組み合わせて有機化合物層を形成することもできる。こ
の場合に使用できるポリマー結合剤としては、ポリスチ
レン、ポリビニルトルエン、ポリ−Ｎ−ビニルカルバゾ
ール、ポリメチルメタクリレート、ポリメチルアクリレ
ート、ポリエステル、ポリカーボネート、ポリアミド等
を挙げることができる。The electroluminescent device of the present invention is one in which a bias is electrically applied to the light emitting layer to cause it to emit light. However, since it may cause a short circuit due to a slight pinhole and the device may not function as a device, the organic compound layer of the organic compound layer is formed. For formation, it is desirable to use a compound having excellent film forming properties together. Further, it is possible to form an organic compound layer by combining a compound having such excellent film-forming property with a polymer binder. Examples of the polymer binder that can be used in this case include polystyrene, polyvinyltoluene, poly-N-vinylcarbazole, polymethylmethacrylate, polymethylacrylate, polyester, polycarbonate and polyamide.
【００１８】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あるいは酸化スズ（Ｓｎ
Ｏ2））、酸化スズ−インジウム（ＩＴＯ）、ヨウ化銅
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）等のポリアルキル
チオフェンやポリピロール、ポリアリーレンビニレン等
の導電性ポリマーなどを用いることができる。金属と導
電性ポリマーの積層体としても良い。一方、陰極材料と
しては、仕事関係の小さな銀、錫、鉛、カルシウム、マ
グネシウム、マンガン、インジウム、アルミニウム、或
はこれらの合金が用いられる。 陽極及び陰極として使
用する材料のうち少なくとも一方は、素子の発光波長領
域において十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。しか
し、端面発光の素子形態をとるときにはむしろ両極とも
光反射率が大きい方が望ましい。As the anode material, nickel, gold, platinum,
Palladium, alloys of these, or tin oxide (Sn
O 2 )), tin oxide-indium (ITO), copper iodide and other metals having a large work function, alloys and compounds thereof,
Further, a polyalkylthiophene such as poly (3-methylthiophene) or a conductive polymer such as polypyrrole or polyarylene vinylene can be used. It may be a laminate of a metal and a conductive polymer. On the other hand, as the cathode material, silver, tin, lead, calcium, magnesium, manganese, indium, aluminum, or alloys thereof having a small work relationship are 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. However, in the case of an edge emitting device, it is preferable that both electrodes have high light reflectance.
【００１９】本発明の電界発光素子は以上の各層をガラ
ス、プラスチックフィルム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、酸素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いれ、
シリコンオイルや乾燥剤等を封入、もしくは、真空セル
中に封入してもよい。The electroluminescent device of the present invention is constructed by laminating each of the above layers on a transparent substrate such as glass or a plastic film in order to form a device, which improves the stability of the device, particularly moisture in the atmosphere. In order to protect against oxygen, a separate protective layer is provided, or the entire device is placed in the cell,
Silicon oil, a desiccant, or the like may be enclosed, or may be enclosed in a vacuum cell.
【００２０】以下、図面に沿って本発明をさらに詳細に
説明する。図１〜７においては、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を設けたものである。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を設けたものである。以
上代表的な構成例について図示したがこれらは最も基本
的な構成例であり、さらに電荷輸送性を向上させるため
の層等が各所に挿入されていても良い。例えば、図５
は、図２において正孔輸送層３ｃが少なくとも２層以上
の層からなる場合であり、図６は、図３において電子輸
送層３ｂが少なくとも２層以上の層からなる場合であ
る。また、図７は、図４において、正孔輸送層と電子輸
送層の何れかもしくは両層が少なくとも２層以上の層か
らなる場合である。また、発光層が複数存在するような
タンデム型積層構成をとる場合にも適用される。また、
本発明においては、透明陽極を透明基板上に形成し、図
１〜図７のような構成とすることが望ましいが、場合に
よっては、その逆構成をとっても良い。The present invention will be described in more detail below with reference to the drawings. 1 to 7, 1 is a substrate, 2 and 4 are electrodes, 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, a light emitting layer 3a is independently provided on the electrode 2, and an electrode is provided thereon. 2 shows an electrode 2 and a light emitting layer 3a in FIG.
The hole transport layer 3c is provided between the two. FIG. 3 shows an electron transport layer 3b provided between the light emitting layer 3a and the electrode 4 in FIG. In FIG. 4, the hole transport layer 3c is provided between the electrode 2 and the light emitting layer 3a in FIG. Although typical configuration examples have been illustrated above, these are the most basic configuration examples, and layers for improving charge transportability may be inserted in various places. For example, in FIG.
2 is a case where the hole transport layer 3c is composed of at least two layers or more in FIG. 2, and FIG. 6 is a case where the electron transport layer 3b is composed of at least two or more layers in FIG. Further, FIG. 7 shows a case where either or both of the hole transport layer and the electron transport layer in FIG. 4 are composed of at least two layers. It is also applied to the case where a tandem type laminated structure having a plurality of light emitting layers is adopted. Also,
In the present invention, it is desirable that the transparent anode is formed on the transparent substrate to have the structure shown in FIGS. 1 to 7, but the reverse structure may be adopted depending on the case.
【００２１】本発明の中で組み合わせて使用される各種
材料については正孔輸送性、電子輸送性、発光性等の機
能を有するものであればいずれのものも使用できるが、
例えば以下に示す従来公知のものが使用できる。As the various materials used in combination in the present invention, any one can be used as long as it has a hole transporting property, an electron transporting property, a light emitting property and the like.
For example, the following conventionally known ones can be used.
【００２２】発光層材料としては、固体において強い蛍
光を有し５０ｎｍ以下の薄膜において緻密な膜を形成す
る物質が好ましい。これまで有機ＥＬ素子の発光層に用
いられてきた従来公知の材料はすべて本発明の有機ＥＬ
素子に適用することができる。たとえば、金属キレート
化オキシノイド化合物（８−ヒドロキシキノリン金属錯
体）（特開昭４９−１９４３９３，特開昭６３−２９５
６９５）、１，４ジフェニルブタジエンおよびテトラフ
ェニルブタジエンのようなブタジエン誘導体、クマリン
誘導体、ベンズオキサゾール誘導体、オキサジアゾール
誘導体、オキサゾール誘導体、チアジアゾール誘導体、
スチリルアミン誘導体、ビススチリルベンゼン誘導体
（特開平２−２４７２７７）、トリススチリルベンゼン
誘導体（特開平３−２９６５９５）、ビススチリルアン
トラセン誘導体（特開平３−１６３１８６）、ペリノン
誘導体、アミノピレン誘導体等は優れた発光層材料であ
る。以下に本発明で有用な発光層材料の具体例について
示す。The material for the light emitting layer is preferably a substance which has strong fluorescence in a solid state and forms a dense film in a thin film of 50 nm or less. All the conventionally known materials that have been used for the light emitting layer of the organic EL device so far are the organic EL of the present invention.
It can be applied to devices. For example, a metal chelated oxinoid compound (8-hydroxyquinoline metal complex) (JP-A-49-194393, JP-A-63-295).
695), butadiene derivatives such as 1,4 diphenyl butadiene and tetraphenyl butadiene, coumarin derivatives, benzoxazole derivatives, oxadiazole derivatives, oxazole derivatives, thiadiazole derivatives,
Styrylamine derivatives, bisstyrylbenzene derivatives (JP-A-2-247277), trisstyrylbenzene derivatives (JP-A-3-296595), bisstyrylanthracene derivatives (JP-A-3-163186), perinone derivatives, aminopyrene derivatives and the like have excellent light emission. It is a layer material. Specific examples of the light emitting layer material useful in the present invention are shown below.
【００２３】[0023]
【表２−（１）】 [Table 2- (1)]
【００２４】[0024]
【表２−（２）】 [Table 2- (2)]
【００２５】[0025]
【表２−（３）】 [Table 2- (3)]
【００２６】正孔輸送層材料としては、これまで正孔輸
送層材料として用いられてきた材料をすべて利用するこ
とができるが、少なくとも２つの芳香族３級アミンを含
み、かつ芳香族３級アミンがモノアリールアミン、ジア
リールアミン、トリアリールアミンである化合物が好ま
しい。このような芳香族３級アミンとして、ＵＳＰＮ
ｏ．４，１７５，９６０、ＵＳＰ Ｎｏ．４，５３９，
５０７、昭６３−２６４６９２によって開示されている
化合物を利用することができる。また、ＵＳＰＮｏ．
４，７２０，４３２に開示されているポルフィリン誘導
体（フタロシアニン類）も有用な化合物である。以下に
有用な正孔輸送層材料の具体例を示す。As the hole transport layer material, all the materials which have been used as the hole transport layer material so far can be used, but at least two aromatic tertiary amines are contained and the aromatic tertiary amine is contained. Compounds in which is a monoarylamine, diarylamine, triarylamine are preferred. As such an aromatic tertiary amine, USPN
o. 4,175,960, USP No. 4,539,
507, the compound disclosed by Sho 63-264692 can be utilized. In addition, USP No.
Porphyrin derivatives (phthalocyanines) disclosed in 4,720,432 are also useful compounds. Specific examples of useful hole transport layer materials are shown below.
【００２７】[0027]
【表３−（１）】 [Table 3- (1)]
【００２８】[0028]
【表３−（２）】 [Table 3- (2)]
【００２９】電子輸送層材料としては、これまで電子輸
送層材料として使用されてきた公知の材料をすべて利用
することができる。１つの好ましい電子輸送材料は、電
子輸送能の発現ユニットであるオキサジアゾール環を少
なくとも１つ以上含む化合物である。代表的な有用なオ
キザジアゾール化合物は、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔ
ｔ５５，１４８９（１９８９）および日本化学会誌１５
４０（１９９１）に開示されている。さらに、本発明の
積層電界発光素子の電子輸送層に使用するために好まし
い有機物質は８−ヒドロキシキノリンのキレートを含め
た金属キレート化オキシノイド化合物である。さらに、
他の好ましい電子輸送層材料としては、１，４−ジフェ
ニルブタジエンおよびテトラフェニルブタジエンのよう
なブタジエン誘導体、クマリン誘導体、ビススチリルベ
ンゼン誘導体、ビススチリルアントラセン誘導体、ベン
ズオキサゾール誘導体、オキサジアゾール誘導体、オキ
サゾール誘導体、チアジアゾール誘導体、ナフタルイミ
ド誘導体、ペリレンテトラカルボン酸ジイミド誘導体、
キナクリドン誘導体等を挙げることができる。以下にこ
れらの具体例を示す。As the electron transport layer material, all known materials which have been used as electron transport layer materials can be used. One preferable electron transporting material is a compound containing at least one oxadiazole ring which is an expression unit having an electron transporting ability. Representative useful oxadiazole compounds are described in Appl. Phys. Let
t55, 1489 (1989) and the Chemical Society of Japan 15
40 (1991). Furthermore, preferred organic materials for use in the electron transport layer of the laminated electroluminescent device of the present invention are metal chelated oxinoid compounds including chelates of 8-hydroxyquinoline. further,
Other preferable electron transport layer materials include butadiene derivatives such as 1,4-diphenylbutadiene and tetraphenylbutadiene, coumarin derivatives, bisstyrylbenzene derivatives, bisstyrylanthracene derivatives, benzoxazole derivatives, oxadiazole derivatives, oxazole derivatives. , Thiadiazole derivative, naphthalimide derivative, perylenetetracarboxylic acid diimide derivative,
Examples thereof include quinacridone derivatives. Specific examples of these are shown below.
【００３０】[0030]
【表４】 [Table 4]
【００３１】[0031]
【実施例】以下、実施例により本発明を更に詳細に説明
する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００３２】実施例１ 表面抵抗２０Ω／□の酸化錫インジウム（ＩＴＯ）陽極
を有するガラス基板上に前記構造式Ａ−２で示されるア
ミノピレン誘導体より成る厚さ５０ｎｍの発光層、前記
構造式Ｄ−４で示される化合物より成る厚さ５０ｎｍの
電子輸送層、原子比１０：１のＭｇＡｇ合金より成る厚
さ２００ｎｍの陰極を順次真空蒸着により積層して図３
に示すような電界発光素子を作製した。蒸着時の真空度
は約０．７×１０-6ｔｏｒｒであり、基板温度は室温で
ある。この様にして作製した素子の陽極及び陰極にリー
ド線を介して直流電源を接続したところ電流密度３０ｍ
Ａ/ｃｍ2において印加電圧が８０Ｖであり、緑色の明瞭
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５１５ｎｍにピークを有し、輝度は３５０ｃｄ/ｍ2
であった。なお、この素子は１ヶ月室温保存後において
も明瞭な発光が認められた。Example 1 On a glass substrate having an indium tin oxide (ITO) anode having a surface resistance of 20 Ω / □, a 50 nm-thick light emitting layer made of the aminopyrene derivative represented by the structural formula A-2, and the structural formula D- An electron transport layer having a thickness of 50 nm made of the compound shown in FIG. 4 and a cathode having a thickness of 200 nm made of a MgAg alloy having an atomic ratio of 10: 1 are sequentially laminated by vacuum vapor deposition.
An electroluminescent device as shown in was prepared. The degree of vacuum during vapor deposition is approximately 0.7 × 10 −6 torr, and the substrate temperature is room temperature. When a direct current power supply was connected to the anode and cathode of the element thus manufactured through lead wires, the current density was 30 m.
At A / cm 2 , the applied voltage was 80 V, and clear green light emission was confirmed for a long time. At this time, the emission wavelength has a peak at 515 nm and the luminance is 350 cd / m 2.
Met. In addition, clear luminescence was recognized even after this device was stored at room temperature for one month.
【００３３】実施例２〜６ 発光層として表５に示す化合物を使用する以外は実施例
１と同様にして図２に示すような電界発光素子を作製し
た。この様にして作製した素子の陽極及び陰極にリード
線を介して直流電源を接続し、評価した結果を表５に示
す。Examples 2 to 6 An electroluminescent device as shown in FIG. 2 was prepared in the same manner as in Example 1 except that the compounds shown in Table 5 were used as the light emitting layer. Table 5 shows the evaluation results obtained by connecting a DC power supply to the anode and cathode of the device thus manufactured through lead wires.
【表５】 なお、これらの素子は１ヶ月室温保存後においても明瞭
な発光が認められた。[Table 5] In addition, clear luminescence was observed in these devices even after storage for one month at room temperature.
【００３４】実施例７ 実施例１と同様にして素子を作製した。ただし、陽極と
発光層の間に構造式Ｃ−１２で示される化合物を含むホ
ール輸送層を５００Å挿入し、発光層膜厚を１５０Å、
電子輸送層膜厚５００Åとし、図４に示す電界発光素子
を作製した。この様にして作製した素子の陽極及び陰極
にリード線を介して直流電源を接続したところ、電流密
度３０ｍＡ／ｃｍ2において印加電圧が７．５Ｖであ
り、緑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５２０ｎｍにピークを有し、輝度は
８６０ｃｄ／ｍ2であった。なお、この素子は１ヶ月室
温保温後においても明瞭な発光が認められた。Example 7 An element was manufactured in the same manner as in Example 1. However, a hole transport layer containing the compound represented by the structural formula C-12 was inserted between the anode and the light emitting layer in an amount of 500 Å, and the thickness of the light emitting layer was 150 Å.
An electron-emitting layer having a film thickness of 500 Å was prepared to produce the electroluminescent device shown in FIG. When a direct current power supply was connected to the anode and cathode of the device thus manufactured through a lead wire, the applied voltage was 7.5 V at a current density of 30 mA / cm 2 , and clear green light emission was confirmed for a long time. Was done.
At this time, the emission wavelength had a peak at 520 nm and the luminance was 860 cd / m 2 . In addition, clear luminescence was recognized even after the device was kept at room temperature for 1 month.
【００３５】実施例８〜１２ 発光層として表６に示す化合物を使用する以外は実施例
７と同様にして図４に示すような電界発光素子を作製し
た。この様にして作製した素子の陽極及び陰極にリード
線を介して直流電源を接続し、評価した結果を表７に示
す。Examples 8 to 12 Electroluminescent devices as shown in FIG. 4 were prepared in the same manner as in Example 7 except that the compounds shown in Table 6 were used as the light emitting layer. Table 7 shows the evaluation results obtained by connecting a DC power supply to the anode and cathode of the device thus manufactured through lead wires.
【表６】 なお、これらの素子は１ヶ月室温保存後においても明瞭
な発光が認められた。[Table 6] In addition, clear luminescence was observed in these devices even after storage for one month at room temperature.
【００３６】実施例１３ ホール輸送層として、構造式Ａ−２で示されるアミノフ
ェニルピレン誘導体を５００Å、発光層として前記構造
式Ｂ−９で示される化合物を５００Å、ＩＴＯ上に実施
例１と同様に形成し、図２に示す電界発光素子を作製し
た。この様にして作製した素子に直流電圧を印加したと
ころ、３０ｍＡ／ｃｍ2の電流密度において、５２０ｃ
ｄ／ｍ2の輝度が観測された。このときの駆動電圧は、
８．５Ｖであった。なお、この素子は１ヶ月室温保存後
においても明瞭な発光が認められた。Example 13 As the hole transport layer, 500 Å of the aminophenylpyrene derivative represented by the structural formula A-2 and 500 Å of the compound represented by the structural formula B-9 as the light emitting layer were formed on the ITO as in Example 1. Then, the electroluminescent device shown in FIG. 2 was manufactured. When a direct current voltage was applied to the device thus manufactured, it was found to be 520c at a current density of 30 mA / cm 2.
A brightness of d / m 2 was observed. The drive voltage at this time is
It was 8.5V. In addition, clear luminescence was recognized even after this device was stored at room temperature for one month.
【００３７】[0037]
【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化１で表される化合物を用い
た事から、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。EFFECT OF THE INVENTION The electroluminescent device of the present invention uses the compound represented by the general formula 1 as a constituent material of an organic compound, and therefore, has a long-lasting luminescent performance and excellent durability. is there.
【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子の模式断面
図である。FIG. 4 is a schematic cross-sectional view of still another electroluminescent device according to the present invention.
【図５】本発明に係る更に別の電界発光素子の模式断面
図である。FIG. 5 is a schematic cross-sectional view of still another electroluminescent device according to the present invention.
【図６】本発明に係る更に別の電界発光素子の模式断面
図である。FIG. 6 is a schematic cross-sectional view of still another electroluminescent device according to the present invention.
【図７】本発明に係る更に別の電界発光素子の模式断面
図である。FIG. 7 is a schematic cross-sectional view of still another electroluminescent device according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 太田 正文 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 Masafumi Ota 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.
Claims (3)
た一層または複数層の有機化合物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）で表される有機化合物
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】 （式中、Ａｒ1、Ａｒ2は置換もしくは無置換のアルキル
基、置換もしくは無置換のアリール基又は置換もしくは
無置換の複素環式芳香環を表す。）1. An electroluminescent device comprising an anode and a cathode and one or a plurality of layers of an organic compound 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 organic compound represented by Chemical formula 1) as a constituent component. [Chemical 1] (In the formula, Ar 1 and Ar 2 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic aromatic ring.)
送層及び一層以上の発光層を構成要素として含有する電
界発光素子あるいは、陽極及び陰極の間に、一層以上の
正孔輸送層及び一層以上の発光層及び一層以上の電子輸
送層を構成要素として含有する電界発光素子において、
前記正孔輸送層のうち少なくとも一層が、請求項１に記
載の一般式（Ｉ）（化１）で表される有機化合物を構成
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 electroluminescent device containing one or more hole-transporting layers and one or more light-emitting layers as constituent elements between an anode and a cathode, or one or more hole-transporting layers between an anode and a cathode. And an electroluminescent device containing one or more light emitting layers and one or more electron transport layers as constituent elements,
At least one layer of the hole transport layer is a layer containing an organic compound represented by the general formula (I) (Chemical formula 1) as a constituent component according to claim 1.
及び一層以上の電子輸送層を構成要素として含有する電
界発光素子、あるいは陽極及び陰極の間に、一層以上の
正孔輸送層及び一層以上の発光層及び一層以上の電子輸
送層を構成要素として含有する電界発光素子、あるいは
陽極及び陰極の間に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、前記発光層のうち少
なくとも一層が、請求項１に記載の一般式（Ｉ）（化
１）で表される有機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 electroluminescent device containing at least one light-emitting layer and at least one electron-transporting layer as constituent elements between an anode and a cathode, or at least one hole-transporting layer between an anode and a cathode. An electroluminescent device comprising one or more light emitting layers and one or more electron transport layers as constituent elements, or an electroluminescent device having an organic single layer device structure in which a light emitting layer is formed between an anode and a cathode, wherein At least one layer among them is a layer containing an organic compound represented by the general formula (I) (formula 1) according to claim 1 as a constituent component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5051545A JPH06240245A (en) | 1993-02-17 | 1993-02-17 | Electroluminescent element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5051545A JPH06240245A (en) | 1993-02-17 | 1993-02-17 | Electroluminescent element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06240245A true JPH06240245A (en) | 1994-08-30 |
Family
ID=12889997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5051545A Pending JPH06240245A (en) | 1993-02-17 | 1993-02-17 | Electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06240245A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996022273A1 (en) * | 1995-01-19 | 1996-07-25 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent element, organic thin film, and triamine compounds |
| WO2001046335A1 (en) * | 1999-12-20 | 2001-06-28 | Matsushita Electric Industrial Co., Ltd. | Thin film el device |
| WO2004044088A1 (en) * | 2002-11-12 | 2004-05-27 | Idemitsu Kosan Co., Ltd. | Material for organic electroluminescent device and organic electroluminescent device using same |
| JP2004158464A (en) * | 1999-12-20 | 2004-06-03 | Matsushita Electric Ind Co Ltd | Thin-film el element |
| JP2006298793A (en) * | 2005-04-18 | 2006-11-02 | Idemitsu Kosan Co Ltd | Aromatic amine derivative and organic electroluminescence element using the same |
| WO2007058127A1 (en) * | 2005-11-16 | 2007-05-24 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescent element using the same |
| US9997713B2 (en) | 2013-01-28 | 2018-06-12 | Samsung Display Co., Ltd. | Organic light-emitting device |
-
1993
- 1993-02-17 JP JP5051545A patent/JPH06240245A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996022273A1 (en) * | 1995-01-19 | 1996-07-25 | Idemitsu Kosan Co., Ltd. | Organic electroluminescent element, organic thin film, and triamine compounds |
| US6989201B2 (en) | 1999-12-20 | 2006-01-24 | Matsushita Electric Industrial Co., Ltd. | Thin film EL device |
| WO2001046335A1 (en) * | 1999-12-20 | 2001-06-28 | Matsushita Electric Industrial Co., Ltd. | Thin film el device |
| US6682832B2 (en) | 1999-12-20 | 2004-01-27 | Matsushita Electric Industrial Co., Ltd. | Thin film el device |
| JP2004158464A (en) * | 1999-12-20 | 2004-06-03 | Matsushita Electric Ind Co Ltd | Thin-film el element |
| KR100476547B1 (en) * | 1999-12-20 | 2005-03-17 | 마쯔시다덴기산교 가부시키가이샤 | Thin film el device |
| WO2004044088A1 (en) * | 2002-11-12 | 2004-05-27 | Idemitsu Kosan Co., Ltd. | Material for organic electroluminescent device and organic electroluminescent device using same |
| CN100343359C (en) * | 2002-11-12 | 2007-10-17 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| US8178218B2 (en) | 2002-11-12 | 2012-05-15 | Idemitsu Kosan Co., Ltd. | Material for organic electroluminescent device and organic electroluminescent device using same |
| JP2006298793A (en) * | 2005-04-18 | 2006-11-02 | Idemitsu Kosan Co Ltd | Aromatic amine derivative and organic electroluminescence element using the same |
| WO2006114949A1 (en) * | 2005-04-18 | 2006-11-02 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescent device using same |
| US7981523B2 (en) | 2005-04-18 | 2011-07-19 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescence device using the same |
| WO2007058127A1 (en) * | 2005-11-16 | 2007-05-24 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescent element using the same |
| US9997713B2 (en) | 2013-01-28 | 2018-06-12 | Samsung Display Co., Ltd. | Organic light-emitting device |
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