JPH06325871A - Organic electroluminescent element - Google Patents
Organic electroluminescent elementInfo
- Publication number
- JPH06325871A JPH06325871A JP5116206A JP11620693A JPH06325871A JP H06325871 A JPH06325871 A JP H06325871A JP 5116206 A JP5116206 A JP 5116206A JP 11620693 A JP11620693 A JP 11620693A JP H06325871 A JPH06325871 A JP H06325871A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- layer
- light emitting
- cathode
- emitting layer
- 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
- 239000000463 material Substances 0.000 abstract description 25
- 230000032258 transport Effects 0.000 abstract description 24
- 150000003377 silicon compounds Chemical class 0.000 abstract description 20
- 230000005684 electric field Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 137
- 230000005525 hole transport Effects 0.000 description 23
- 239000000758 substrate Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 239000010408 film Substances 0.000 description 14
- 238000007740 vapor deposition Methods 0.000 description 14
- 150000003961 organosilicon compounds Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- -1 poly (p-phenylene vinylene) Polymers 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000005401 electroluminescence Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229960003540 oxyquinoline Drugs 0.000 description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-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 1
- SULWTXOWAFVWOY-PHEQNACWSA-N 2,3-bis[(E)-2-phenylethenyl]pyrazine Chemical class C=1C=CC=CC=1/C=C/C1=NC=CN=C1\C=C\C1=CC=CC=C1 SULWTXOWAFVWOY-PHEQNACWSA-N 0.000 description 1
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 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
- 239000010931 gold Substances 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CELAVSIYCCQNGG-UHFFFAOYSA-N n-(4-cyclohexylphenyl)-4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1CCCCC1)C1=CC=C(C)C=C1 CELAVSIYCCQNGG-UHFFFAOYSA-N 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer 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
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000005255 pyrrolopyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical class C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は有機電界発光素子に関す
るものであり、詳しくは、有機化合物から成る発光層に
電界をかけて光を放出する薄膜型デバイスに関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device, and more particularly, to a thin film type device which emits light by applying an electric field to a light emitting layer made of an organic compound.
【0002】[0002]
【従来の技術】従来、薄膜型の電界発光素子としては、
無機材料のII−VI族化合物半導体であるZnS、Ca
S、SrS等に、発光中心であるMnや希土類元素(E
u、Ce、Tb、Sm等)をドープしたものが一般的で
あるが、上記の無機材料から作製した電界発光素子は、
1)交流駆動が必要(50〜1000Hz)、2)駆動
電圧が高い(〜200V)、3)フルカラー化が困難
(特に青色が問題)、4)周辺駆動回路のコストが高
い、という問題点を有している。2. Description of the Related Art Conventionally, as a thin film type electroluminescent device,
ZnS and Ca which are II-VI group compound semiconductors of inorganic materials
In S, SrS, etc., Mn, which is the emission center, and rare earth elements (E
(u, Ce, Tb, Sm, etc.) is generally doped, but an electroluminescent device made of the above inorganic material is
1) AC drive is required (50 to 1000 Hz), 2) High drive voltage (up to 200 V), 3) Full colorization is difficult (especially blue color is a problem), and 4) Peripheral drive circuit cost is high. Have
【0003】しかし、近年、上記問題点の改良のため、
有機薄膜を用いた電界発光素子の開発が行われるように
なった。特に、発光効率を高めるために電極からのキャ
リアー注入の効率向上を目的とした電極種類の最適化を
行い、芳香族ジアミンから成る有機正孔輸送層と8−ヒ
ドロキシキノリンのアルミニウム錯体から成る発光層を
設けた有機電界発光素子の開発(Appl.Phys.
Lett.,51巻,913頁,1987年)により、
従来のアントラセン等の単結晶を用いた電界発光素子と
比較して発光効率の大幅な改善がなされている。However, in recent years, in order to improve the above problems,
Electroluminescent devices using organic thin films have been developed. In particular, the electrode type was optimized for the purpose of improving the efficiency of carrier injection from the electrode in order to increase the light emission efficiency, and an organic hole transport layer composed of an aromatic diamine and a light emitting layer composed of an aluminum complex of 8-hydroxyquinoline. Of an organic electroluminescent device provided with (Appl. Phys.
Lett. , 51, 913, 1987),
Compared with the conventional electroluminescent device using a single crystal such as anthracene, the luminous efficiency has been significantly improved.
【0004】また、有機発光層としては、ポリ(p−フ
ェニレンビニレン)(Nature,347巻,539
頁,1990年;Appl.Phys.Lett.,6
1巻,2793頁,1992年)、ポリ[2−メトキ
シ,5−(2’−エチルヘキソキシ)−1,4−フェニ
レンビニレン](Appl.Phys.Lett.,5
8巻,1982頁,1991年;Thin Solid
Films,216巻,96頁,1992年;Nat
ure,357巻,477頁,1992年)、ポリ(3
−アルキルチオフェン)(Jpn.J.Appl.Ph
ys,30巻,L1938頁,1991年;J.App
l.Phys.,72巻,564頁,1992年)等の
高分子材料の開発や、ポリビニルカルバゾール等の高分
子に発光材料と電子移動材料を混合した素子(応用物
理,61巻,1044頁,1992年)も開発されてい
る。As the organic light emitting layer, poly (p-phenylene vinylene) (Nature, Volume 347, 539) is used.
P., 1990; Appl. Phys. Lett. , 6
1, 2793, 1992), poly [2-methoxy, 5- (2'-ethylhexoxy) -1,4-phenylenevinylene] (Appl. Phys. Lett., 5).
Volume 8, 1982, 1991; Thin Solid.
Films, 216, 96, 1992; Nat
ure, 357, p. 477, 1992), poly (3
-Alkylthiophene) (Jpn.J.Appl.Ph)
ys, vol. 30, L1938, 1991; App
l. Phys. , 72, 564, 1992), etc., and development of polymer materials such as polyvinylcarbazole and luminescent materials and electron transfer materials (applied physics, 61, 1044, 1992). Being developed.
【0005】以上に示した様な有機電界発光素子におい
ては、通常、陽極としてはインジウム錫酸化物(IT
O)のような透明電極が用いられるが、陰極に関しては
電子注入を効率よく行うために仕事関数の低い金属電極
が用いられ、マグネシウム合金やカルシウム等が使われ
ている。有機電界発光素子の最大の問題点は素子の寿命
であり、寿命を制限する一つの要因が陰極材料に由来す
るダークスポット(素子の発光部で発光しない部分をさ
す)の発生である。このために、長期間保存する場合
に、有機電界発光素子内のダークスポットの数・大きさ
が増加して、結果として素子の寿命が短いものとなって
いる。In the organic electroluminescent device as described above, indium tin oxide (IT) is usually used as the anode.
Although a transparent electrode such as O) is used, a metal electrode having a low work function is used for the cathode in order to efficiently inject electrons, and magnesium alloy, calcium or the like is used. The biggest problem of the organic electroluminescence device is the life of the device, and one of the factors that limits the life is the occurrence of dark spots (indicating the part of the device that does not emit light) due to the cathode material. For this reason, the number and size of dark spots in the organic electroluminescent device increase when the device is stored for a long period of time, resulting in a shorter device life.
【0006】[0006]
【発明が解決しようとする課題】これまでに開示されて
いる有機電界発光素子では、電界発光は陽極から注入さ
れた正孔と陰極から注入された電子との再結合によりも
たらされる。一般に、キャリアの注入は、電子の場合、
陰極と有機発光層との界面における注入障壁を乗り越え
て行われなければならない。この電子注入障壁を低くし
て注入効率を向上させるために、マグネシウム合金やカ
ルシウム等の低仕事関数の金属電極が陰極として使用さ
れている。しかしながら、これらの金属材料は有機発光
層との密着性が悪いために、陰極が有機発光層から剥
離、又は、酸化して、長期間の保存中に素子の発光特性
が劣化したり、ダークスポットが発生することが問題と
なっていた。素子を作製する時に基板加熱を行ったり、
作製した後で加熱処理して、陰極と有機発光層との間の
密着性を向上させることは可能ではあるが、加熱の際に
陰極と有機発光層との間で反応がおき、発光特性の低下
が避けられなかった。In the organic electroluminescent devices disclosed so far, electroluminescence is brought about by the recombination of holes injected from the anode and electrons injected from the cathode. In general, the injection of carriers is
It must be done by overcoming the injection barrier at the interface between the cathode and the organic light emitting layer. In order to lower the electron injection barrier and improve the injection efficiency, a low work function metal electrode such as magnesium alloy or calcium is used as the cathode. However, since these metal materials have poor adhesion to the organic light emitting layer, the cathode is peeled from the organic light emitting layer, or is oxidized, and the light emitting characteristics of the device are deteriorated during long-term storage, or dark spots are generated. Was a problem. The substrate is heated when the device is manufactured,
Although it is possible to improve the adhesion between the cathode and the organic light-emitting layer by heat treatment after the production, a reaction occurs between the cathode and the organic light-emitting layer during heating, and The decline was unavoidable.
【0007】[0007]
【課題を解決するための手段】本発明者等は上記実状に
鑑み、長期間に渡って安定な発光特性を維持でき、ダー
クスポットの発生を抑制することができ、陰極との密着
性向上のための加熱処理に耐えうる有機電界発光素子を
提供することを目的として鋭意検討した結果、有機発光
層と陰極の間に有機シリコン化合物を含有する界面層を
設けることが好適であることを見い出し、本発明を完成
するに至った。In view of the above situation, the present inventors have been able to maintain stable emission characteristics for a long period of time, suppress the generation of dark spots, and improve the adhesion to the cathode. As a result of extensive studies for the purpose of providing an organic electroluminescent element that can withstand heat treatment for, it was found that it is preferable to provide an interface layer containing an organic silicon compound between the organic light emitting layer and the cathode, The present invention has been completed.
【0008】即ち、本発明の要旨は、陽極、有機発光
層、陰極を積層した有機電界発光素子であって、有機発
光層と陰極との間に有機シリコン化合物を含有する界面
層を設けたことを特徴とする有機電界発光素子に存す
る。以下、本発明の有機電界発光素子について図面に従
い説明する。図1は、本発明の有機電界発光素子の構造
例を模式的に示す断面図であり、1は基板、2a、2b
は導電層、3は有機発光層、4は界面層を各々表わす。That is, the gist of the present invention is an organic electroluminescent device in which an anode, an organic light emitting layer, and a cathode are laminated, and an interface layer containing an organic silicon compound is provided between the organic light emitting layer and the cathode. The present invention resides in an organic electroluminescent device. Hereinafter, the organic electroluminescent device of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing a structural example of the organic electroluminescence device of the present invention, in which 1 is a substrate, 2a and 2b.
Represents a conductive layer, 3 represents an organic light emitting layer, and 4 represents an interface layer.
【0009】基板1は、本発明の有機電界発光素子の支
持体となるものであり、石英やガラスの板、金属板や金
属箔、プラスチックフィルムやシート等が用いられる
が、ガラス板や、ポリエステル、ポリメタアクリレー
ト、ポリカーボネート、ポリサルホン等の透明な合成樹
脂基板が好ましい。基板1上には導電層2aが設けられ
るが、この導電層2aとしては通常、アルミニウム、
金、銀、ニッケル、パラジウム、テルル等の金属、イン
ジウム及び/又はスズの酸化物等の金属酸化物やヨウ化
銅、カーボンブラック、あるいは、ポリ(3−メチルチ
オフェン)等の導電性高分子等により構成される。導電
層の形成は通常、スパッタリング法、真空蒸着法等によ
り行われることが多いが、銀等の金属微粒子あるいはヨ
ウ化銅、カーボンブラック、導電性の金属酸化物微粒
子、導電性高分子微粉末等の場合には、適当なバインダ
ー樹脂溶液に分散し、基板上に塗布することにより形成
することもできる。さらに、導電性高分子の場合は電解
重合により直接基板上に薄膜を形成したり、基板上に塗
布して形成することもできる(Appl.Phys.L
ett.,60巻,2711頁,1992年)。導電層
2aの厚みは、必要とする透明性により異なるが、透明
性が必要とされる場合は、可視光の透過率が60%以
上、好ましくは80%以上であることが望ましく、この
場合、厚みは、通常、5〜1000nm、好ましくは1
0〜500nm程度である。The substrate 1 serves as a support for the organic electroluminescence device of the present invention, and a plate of quartz or glass, a metal plate or metal foil, a plastic film or sheet, etc. is used, but a glass plate or polyester. A transparent synthetic resin substrate such as polymethacrylate, polycarbonate, or polysulfone is preferable. A conductive layer 2a is provided on the substrate 1. The conductive layer 2a is usually aluminum,
Metals such as gold, silver, nickel, palladium, tellurium, metal oxides such as oxides of indium and / or tin, copper iodide, carbon black, and conductive polymers such as poly (3-methylthiophene) It is composed of The conductive layer is usually formed by a sputtering method, a vacuum deposition method or the like, but fine particles of metal such as silver or copper iodide, carbon black, fine particles of conductive metal oxide, fine powder of conductive polymer, etc. In this case, it can also be formed by dispersing it in an appropriate binder resin solution and applying it on a substrate. Further, in the case of a conductive polymer, a thin film can be directly formed on the substrate by electrolytic polymerization or can be formed by coating on the substrate (Appl. Phys. L).
ett. , 60, 2711, 1992). The thickness of the conductive layer 2a varies depending on the required transparency, but when the transparency is required, it is desirable that the visible light transmittance is 60% or more, preferably 80% or more. The thickness is usually 5 to 1000 nm, preferably 1
It is about 0 to 500 nm.
【0010】不透明でよい場合は導電層2aは基板1と
同一でもよい。また、さらには上記の導電層を異なる物
質を積層することも可能である。図1の例では、導電層
2aは陽極(アノード)として正孔注入の役割を果たす
ものである。一方、導電層2bは陰極(カソード)とし
て、界面層4を通して有機発光層3に電子を注入する役
割を果たす。導電層2bとして用いられる材料は、前記
導電層2a用の材料を用いることが可能であるが、効率
よく電子注入を行なうには、仕事関数の低い金属が好ま
しく、スズ、マグネシウム、インジウム、アルミニウ
ム、銀等の適当な金属又はそれらの合金が用いられる。
導電層2bの膜厚は通常、導電層2aと同様である。ま
た、図1には示してはいないが、導電層2bの上にさら
に基板1と同様の基板を設けることもできる。但し、導
電層2aと2bの少なくとも一方は透明性の良いことが
電界発光素子としては必要である。このことから、導電
層2aと2bのうちどちらか一方は、10〜500nm
の膜厚であることが好ましく、透明性の良いことが望ま
れる。The conductive layer 2a may be the same as the substrate 1 if it is opaque. Further, it is also possible to stack different materials on the above conductive layers. In the example of FIG. 1, the conductive layer 2a plays a role of hole injection as an anode. On the other hand, the conductive layer 2b serves as a cathode to inject electrons into the organic light emitting layer 3 through the interface layer 4. The material used for the conductive layer 2b can be the material for the conductive layer 2a, but a metal having a low work function is preferable for efficient electron injection, and tin, magnesium, indium, aluminum, A suitable metal such as silver or an alloy thereof is used.
The thickness of the conductive layer 2b is usually the same as that of the conductive layer 2a. Although not shown in FIG. 1, a substrate similar to the substrate 1 may be further provided on the conductive layer 2b. However, it is necessary for at least one of the conductive layers 2a and 2b that the electroluminescent element has good transparency. From this, one of the conductive layers 2a and 2b has a thickness of 10 to 500 nm.
It is preferable that the film thickness is, and good transparency is desired.
【0011】導電層2aの上には有機発光層3が設けら
れるが、有機発光層3は、電界を与えられた電極間にお
いて、陽極から注入された正孔と陰極から注入された電
子がを効率よく輸送して再結合させ、かつ、再結合によ
り効率よく発光する材料から形成される。通常、この有
機発光層3は発光効率の向上のために、図2に示すよう
に、正孔輸送層3aと電子輸送層3bに分割して機能分
離型にすることが行われる(Appl.Phys.Le
tt.,51巻,913頁,1987年)。An organic light emitting layer 3 is provided on the conductive layer 2a. The organic light emitting layer 3 has holes injected from the anode and electrons injected from the cathode between the electrodes to which an electric field is applied. It is formed from a material that efficiently transports and recombines, and that recombination efficiently emits light. Usually, in order to improve the luminous efficiency, the organic light emitting layer 3 is divided into a hole transporting layer 3a and an electron transporting layer 3b so as to have a function separation type (Appl. Phys). . Le
tt. , 51, 913, 1987).
【0012】上記の機能分離型素子において、正孔輸送
材料としては、導電層2aからの正孔注入効率が高く、
かつ、注入された正孔を効率よく輸送することができる
材料であることが必要である。そのためには、イオン化
ポテンシャルが小さく、しかも正孔移動度が大きく、さ
らに安定性にすぐれ、トラップとなる不純物が製造時や
使用時に発生しにくいことが要求される。In the above-mentioned function-separated device, the hole transport material has a high hole injection efficiency from the conductive layer 2a,
At the same time, it is necessary that the material is capable of efficiently transporting the injected holes. For that purpose, it is required that the ionization potential is small, the hole mobility is large, the stability is excellent, and the impurities serving as traps are not easily generated during manufacturing or use.
【0013】このような正孔輸送化合物としては、例え
ば、特開昭59−194393号公報、米国特許第4,
175,960号、米国特許第4,923,774号及
び米国特許第5,047,687号に解説される、N,
N’−ジフェニル−N,N’−(3−メチルフェニル)
−1,1’−ビフェニル−4,4’−ジアミン:1,
1’−ビス(4−ジ−p−トリルアミノフェニル)シク
ロヘキサン:4,4’−ビス(ジフェニルアミノ)クワ
ドロフェニル等の芳香族アミン系化合物、特開平2−3
11591号公報に示されるヒドラゾン化合物、米国特
許第4,950,950号公報に示されるシラザン化合
物、キナクリドン化合物等が挙げられる。これらの化合
物は、単独で用いるか、必要に応じて、各々、混合して
用いてもよい。上記の化合物以外に、ポリビニルカルバ
ゾールやポリシラン(Appl.Phys.Let
t.,59巻,2760頁,1991年)等の高分子材
料が挙げられる。Examples of such hole transport compounds include, for example, JP-A-59-194393, US Pat.
175,960, U.S. Pat. No. 4,923,774 and U.S. Pat. No. 5,047,687, N,
N'-diphenyl-N, N '-(3-methylphenyl)
-1,1'-biphenyl-4,4'-diamine: 1,
Aromatic amine compounds such as 1'-bis (4-di-p-tolylaminophenyl) cyclohexane: 4,4'-bis (diphenylamino) quadrophenyl, JP-A 2-3
The hydrazone compound shown in 11591 gazette, the silazane compound shown by US Patent 4,950,950, a quinacridone compound, etc. are mentioned. These compounds may be used alone or, if necessary, may be mixed and used. In addition to the above compounds, polyvinylcarbazole and polysilane (Appl. Phys. Let)
t. , Vol. 59, page 2760, 1991) and the like.
【0014】上記の有機正孔輸送材料は塗布法あるいは
真空蒸着法により前記導電層2a上に積層することによ
り正孔輸送層3aを形成する。塗布の場合は、有機正孔
輸送化合物を1種又は2種以上と必要により正孔のトラ
ップにならないバインダー樹脂や、レベリング剤等の塗
布性改良剤等の添加剤を添加し溶解した塗布溶液を調整
し、スピンコート法等の方法により導電層2a上に塗布
し、乾燥して有機正孔輸送層3を形成する。バインダー
樹脂としては、ポリカーボネート、ポリアリレート、ポ
リエステル等が挙げられる。バインダー樹脂は添加量が
多いと正孔移動度を低下させるので、少ない方が望まし
く、50重量%以下が好ましい。The organic hole transport material is laminated on the conductive layer 2a by a coating method or a vacuum deposition method to form the hole transport layer 3a. In the case of coating, a coating solution prepared by adding and dissolving one or more organic hole-transporting compounds, if necessary, a binder resin that does not trap holes and a coating property improving agent such as a leveling agent is dissolved. The organic hole transport layer 3 is formed by adjusting, coating the conductive layer 2a on the conductive layer 2a by a method such as spin coating, and drying. Examples of the binder resin include polycarbonate, polyarylate, polyester and the like. The addition amount of the binder resin decreases the hole mobility when it is added in a large amount. Therefore, it is preferable that the addition amount is 50% by weight or less.
【0015】真空蒸着法の場合には、有機正孔輸送材料
を真空容器内に設置されたルツボに入れ、真空容器内を
適当な真空ポンプで10-6Torrにまで排気した後、
ルツボを加熱して、正孔輸送材料を蒸発させ、ルツボと
向き合って置かれた基板上に層を形成する。正孔輸送層
3aの膜厚は、通常、10〜300nm、好ましくは3
0〜100nmである。この様に薄い膜を一様に形成す
るためには、真空蒸着法がよく用いられる。In the case of the vacuum deposition method, the organic hole transporting material is placed in a crucible installed in a vacuum container, the interior of the vacuum container is evacuated to 10 −6 Torr by an appropriate vacuum pump,
The crucible is heated to evaporate the hole transport material and form a layer on the substrate placed facing the crucible. The thickness of the hole transport layer 3a is usually 10 to 300 nm, preferably 3
It is 0 to 100 nm. In order to uniformly form such a thin film, the vacuum evaporation method is often used.
【0016】正孔輸送層3aの材料としては有機化合物
の代わりに無機材料を使用することも可能である。無機
材料に要求される条件は、有機正孔輸送化合物と同じで
ある。正孔輸送層3に用いられる無機材料としては、p
型水素化非晶質シリコン、p型水素化非晶質炭化シリコ
ン、p型水素化微結晶性炭化シリコン、あるいは、p型
硫化亜鉛、p型セレン化亜鉛等が挙げられる。これらの
無機正孔輸送層はCVD法、プラズマCVD法、真空蒸
着法、スパッタ法等により形成される。As the material of the hole transport layer 3a, it is possible to use an inorganic material instead of the organic compound. The conditions required for the inorganic material are the same as those for the organic hole transport compound. The inorganic material used for the hole transport layer 3 is p
Examples thereof include p-type hydrogenated amorphous silicon, p-type hydrogenated amorphous silicon carbide, p-type hydrogenated microcrystalline silicon carbide, p-type zinc sulfide, and p-type zinc selenide. These inorganic hole transport layers are formed by a CVD method, a plasma CVD method, a vacuum deposition method, a sputtering method, or the like.
【0017】無機正孔輸送層の膜厚も有機正孔輸送層と
同様に、通常、10〜300nm、好ましくは30〜1
00nmである。正孔輸送層3aの上には電子輸送層3
bが設けられるが、電子輸送層3bは、電界を与えられ
た電極間において陰極からの電子を効率よく正孔輸送層
の方向に輸送することができる化合物より形成される。The thickness of the inorganic hole transporting layer is usually 10 to 300 nm, preferably 30 to 1 like the organic hole transporting layer.
00 nm. The electron transport layer 3 is formed on the hole transport layer 3a.
b is provided, the electron transport layer 3b is formed of a compound capable of efficiently transporting electrons from the cathode toward the hole transport layer between the electrodes to which an electric field is applied.
【0018】有機電子輸送化合物としては、導電層2b
からの電子注入効率が高く、かつ、注入された電子を効
率よく輸送することができる化合物であることが必要で
ある。そのためには、電子親和力が大きく、しかも電子
移動度が大きく、さらに安定性にすぐれトラップとなる
不純物が製造時や使用時に発生しにくい化合物であるこ
とが要求される。As the organic electron transport compound, the conductive layer 2b is used.
It is necessary that the compound has a high efficiency of injecting electrons from the compound and can efficiently transport the injected electrons. For that purpose, it is required that the compound has a high electron affinity, a high electron mobility, excellent stability, and an impurity that becomes a trap and is less likely to be generated at the time of production or use.
【0019】このような条件を満たす材料としては、テ
トラフェニルブタジエン等の芳香族化合物(特開昭57
−51781号公報)、8−ヒドロキシキノリンのアル
ミニウム錯体等の金属錯体(特開昭59−194393
号公報)、シクロペンタジエン誘導体(特開平2−28
9675号公報)、ペリノン誘導体(特開平2−289
676号公報)、オキサジアゾール誘導体(特開平2−
216791号公報)、ビススチリルベンゼン誘導体
(特開平1−245087号公報、同2−222484
号公報)、ペリレン誘導体(特開平2−189890号
公報、同3−791号公報)、クマリン化合物(特開平
2−191694号公報、同3−792号公報)、希土
類錯体(特開平1−256584)、ジスチリルピラジ
ン誘導体(特開平2−252793号公報)、p−フェ
ニレン化合物(特開平3−33183号公報)、チアジ
アゾロピリジン誘導体(特開平3−37292号公
報)、ピロロピリジン誘導体(特開平3−37293号
公報)、ナフチリジン誘導体(特開平3−203982
号公報)等が挙げられる。これらの化合物を用いた有機
電子輸送層は、電子を輸送する役割と、正孔と電子の再
結合の際に発光をもたらす役割を同時に果しており、発
光層を兼ねている。As a material satisfying such a condition, an aromatic compound such as tetraphenyl butadiene (Japanese Patent Application Laid-Open No. 57-57242)
No. 51781), a metal complex such as an aluminum complex of 8-hydroxyquinoline (JP-A-59-194393).
JP), a cyclopentadiene derivative (JP-A-2-28)
9675), perinone derivatives (JP-A-2-289)
676), oxadiazole derivatives (JP-A-2-
No. 216791), and bisstyrylbenzene derivatives (JP-A Nos. 1-245087 and 2-222484).
No.), perylene derivatives (JP-A-2-189890, JP-A-3-791), coumarin compounds (JP-A-2-191694, JP-A-3-792), and rare earth complexes (JP-A-1-256584). ), Distyrylpyrazine derivative (JP-A-2-252793), p-phenylene compound (JP-A-3-33183), thiadiazolopyridine derivative (JP-A-3-37292), pyrrolopyridine derivative (special Kaihei 3-37293) and naphthyridine derivatives (JP-A-3-203982).
Gazette) and the like. The organic electron transporting layer using these compounds plays a role of transporting electrons and a role of causing light emission upon recombination of holes and electrons, and also serves as a light emitting layer.
【0020】有機正孔輸送化合物が発光機能を有する場
合は、有機電子輸送層は電子を輸送する役割だけを果た
す。素子の発光効率を向上させるとともに発光色を変え
る目的で、例えば、8−ヒドロキシキノリンのアルミニ
ウム錯体をホスト材料として、クマリン等のレーザ用蛍
光色素をドープすること(J.Appl.Phys.,
65巻,3610頁,1989年)も行われている。本
発明においても上記の有機電子輸送材料をホスト材料と
して各種の蛍光色素を10-3〜10モル%ドープするこ
とにより、素子の発光特性をさらに向上させることがで
きる。電子輸送層3bの膜厚は、通常、10〜200n
m、好ましくは30〜100nmである。When the organic hole transport compound has a light emitting function, the organic electron transport layer serves only to transport electrons. For the purpose of improving the luminous efficiency of the device and changing the luminescent color, for example, by doping an aluminum complex of 8-hydroxyquinoline as a host material with a fluorescent dye for laser such as coumarin (J. Appl. Phys.,
65, 3610, 1989). Also in the present invention, the emission characteristics of the device can be further improved by doping the above-mentioned organic electron transport material as a host material with various fluorescent dyes at 10 −3 to 10 mol%. The thickness of the electron transport layer 3b is usually 10 to 200 n.
m, preferably 30 to 100 nm.
【0021】有機電子輸送層も有機正孔輸送層と同様の
方法で形成することができるが、通常は真空蒸着法が用
いられる。有機電界発光素子の発光効率をさらに向上さ
せる方法として、電子輸送層3bの上にさらに他の電子
輸送層3cを積層することが考えられる(図3参照)。
この電子輸送層3cに用いられる化合物には、陰極から
の電子注入が容易で、電子の輸送能力がさらに大きいこ
とが要求される。この様な電子輸送材料としては、The organic electron transport layer can also be formed by the same method as that for the organic hole transport layer, but the vacuum deposition method is usually used. As a method for further improving the luminous efficiency of the organic electroluminescent device, it is conceivable to stack another electron transport layer 3c on the electron transport layer 3b (see FIG. 3).
The compound used for the electron transport layer 3c is required to be capable of easily injecting electrons from the cathode and have a higher electron transport capability. As such an electron transport material,
【0022】[0022]
【化1】 [Chemical 1]
【0023】[0023]
【化2】 [Chemical 2]
【0024】等のオキサジアゾール誘導体(Appl.
Phys.Lett.,55巻,1489頁,1989
年;Jpn.J.Appl.Phys.,31巻,18
12頁,1992年)やそれらをポリメチルメタクリレ
ート等の樹脂に分散した系(Appl.Phys.Le
tt.,61巻,2793頁,1992年)、又は、n
型水素化非晶質炭化シリコン、n型硫化亜鉛、n型セレ
ン化亜鉛等が挙げられる。電子輸送層3cの膜厚は、通
常、5〜200nm、好ましくは10〜100nmであ
る。Oxadiazole derivatives such as (Appl.
Phys. Lett. , 55, 1489, 1989
Year; Jpn. J. Appl. Phys. , Volume 31, 18
P. 12, 1992) or a system in which they are dispersed in a resin such as polymethylmethacrylate (Appl. Phys. Le.
tt. , 61, 2793, 1992), or n
Examples include hydrogenated amorphous silicon carbide, n-type zinc sulfide, and n-type zinc selenide. The thickness of the electron transport layer 3c is usually 5 to 200 nm, preferably 10 to 100 nm.
【0025】また、機能分離を行わない単層型の有機発
光層3としては、先に挙げたポリ(p−フェニレンビニ
レン)(Nature,347巻,539頁,1990
年;Appl.Phys.Lett.,61巻,279
3頁,1992年)、ポリ[2−メトキシ,5−(2’
−エチルヘキソキシ)−1,4−フェニレンビニレン]
(Appl.Phys.Lett.,58巻,1982
頁,1991年;Thin Solid Films,
216巻,96頁,1992年;Nature,357
巻,477頁,1992年)、ポリ(3−アルキルチオ
フェン)(Jpn.J.Appl.Phys,30巻,
L1938頁,1991年;J.Appl.Phy
s.,72巻,564頁,1992年)等の高分子材料
や、ポリビニルカルバゾール等の高分子に発光材料と電
子移動材料を混合した系(応用物理,61巻,1044
頁,1992年)がある。As the single-layer type organic light emitting layer 3 which does not perform the function separation, the above-mentioned poly (p-phenylene vinylene) (Nature, 347, 539, 1990) is used.
Year; Appl. Phys. Lett. , Volume 61, 279
P. 3, 1992), poly [2-methoxy, 5- (2 '
-Ethylhexoxy) -1,4-phenylene vinylene]
(Appl. Phys. Lett., 58, 1982.
P., 1991; Thin Solid Films,
216, 96, 1992; Nature, 357.
Vol., 477, 1992), poly (3-alkylthiophene) (Jpn. J. Appl. Phys, vol. 30,
L 1938, 1991; Appl. Phy
s. , Vol. 72, p. 564, 1992), or a system in which a light emitting material and an electron transfer material are mixed with a polymer such as polyvinylcarbazole (Applied Physics, 61, 1044).
Page, 1992).
【0026】有機発光層の上に界面層4が設けられる。
界面層の役割としては、有機発光層との親和性があると
同時に陰極との密着性がよく、かつ、化学的に安定で陰
極形成時及び/又は形成後の有機発光層と陰極の反応を
抑制する効果を有することが挙げられる。また、均一な
薄膜形状を与えることも陰極との密着性の点で重要であ
る。本発明者らは、このような役割を果たす材料とし
て、有機シリコン化合物が好適であることを見い出し
た。An interface layer 4 is provided on the organic light emitting layer.
The role of the interface layer is that it has an affinity with the organic light-emitting layer and at the same time has good adhesion to the cathode, and is chemically stable to allow the reaction between the organic light-emitting layer and the cathode during and / or after formation of the cathode. It has a suppressing effect. It is also important to provide a uniform thin film shape from the viewpoint of adhesion with the cathode. The present inventors have found that an organic silicon compound is suitable as a material that plays such a role.
【0027】有機シリコン化合物から成る界面層は、前
述の有機正孔輸送材料と同様に、塗布法あるいは真空蒸
着法により形成される。本発明においては、以上の様
に、有機電界発光素子における有機発光層と陰極との間
の界面層材料として、有機シリコン化合物を用いること
により、優れた素子の安定性が達成される。The interface layer made of an organic silicon compound is formed by a coating method or a vacuum vapor deposition method, like the organic hole transporting material described above. In the present invention, as described above, excellent device stability is achieved by using an organic silicon compound as an interface layer material between the organic light emitting layer and the cathode in the organic electroluminescent device.
【0028】界面層に用いられる有機シリコン化合物と
しては、シリコン原子を含有する有機シリコン化合物な
ら利用できるが、好ましくは含芳香族シリコン化合物、
さらには、シリコン原子に芳香環が結合した有機シリコ
ン化合物である。具体例を以下の構造式(1)〜(8)
に示すが、これらに限定するものではない。As the organic silicon compound used for the interface layer, any organic silicon compound containing a silicon atom can be used, but preferably an aromatic silicon compound containing an aromatic silicon compound,
Further, it is an organic silicon compound in which an aromatic ring is bonded to a silicon atom. Specific examples are the following structural formulas (1) to (8)
However, the present invention is not limited to these.
【0029】[0029]
【化3】 [Chemical 3]
【0030】[0030]
【化4】 [Chemical 4]
【0031】上記に示した有機シリコン化合物を界面層
として形成する場合、これらの化合物同士をさらに混合
して用いてもよい。有機シリコン化合物から成る界面層
を有する本発明における有機電界発光素子は、以下に示
すような層構成のものが挙げられる。When the organic silicon compound shown above is formed as the interface layer, these compounds may be further mixed and used. The organic electroluminescent device of the present invention having an interface layer made of an organic silicon compound may have the following layer structure.
【0032】[0032]
【表1】 陽極/有機発光層/界面層/陰極、 陽極/高分子から成る有機発光層/界面層/陰極、 陽極/高分子に分散させた有機発光層/界面層/陰極、 陽極/正孔輸送層/有機電子輸送性発光層/界面層/陰
極、 陽極/有機正孔輸送性発光層/有機電子輸送層/界面層
/陰極、 陽極/正孔輸送層/有機電子輸送性発光層/電子輸送層
/界面層/陰極、 界面層4の膜厚は、通常、2〜100nm、好ましくは
5〜30nmである。[Table 1] Anode / organic light-emitting layer / interface layer / cathode, anode / polymer organic light-emitting layer / interface layer / cathode, anode / polymer dispersed organic light-emitting layer / interface layer / cathode, anode / positive Pore transport layer / organic electron transport light emitting layer / interface layer / cathode, anode / organic hole transport light emitting layer / organic electron transport layer / interface layer / cathode, anode / hole transport layer / organic electron transport light emitting layer / The thickness of the electron transport layer / interface layer / cathode and interface layer 4 is usually 2 to 100 nm, preferably 5 to 30 nm.
【0033】上記の各層構成において、界面層として有
機発光層、有機電子輸送性発光層、有機電子輸送層又は
電子輸送層の陰極界面近傍に有機シリコン化合物を50
モル%以上含む領域(層)を設けてもよい。本発明にお
いては、有機電界発光素子における有機発光層と陰極と
の間の界面層として、有機シリコン化合物を50モル%
以上含有する層を設けることにより、優れた素子の安定
性が達成されるのである。In each of the above layer structures, an organic silicon compound is added as an interface layer in the vicinity of the cathode interface of the organic light emitting layer, the organic electron transporting light emitting layer, the organic electron transporting layer or the electron transporting layer.
A region (layer) containing at least mol% may be provided. In the present invention, 50 mol% of an organic silicon compound is used as an interface layer between the organic light emitting layer and the cathode in the organic electroluminescent device.
By providing the above-described layers, excellent device stability is achieved.
【0034】尚、図1とは逆の構造、即ち、基板上に導
電層2b、界面層4、有機発光層3、導電層2aの順に
積層することも可能であり、既述した様に少なくとも一
方が透明性の高い2枚の基板の間に本発明の有機電界発
光素子を設けることも可能である。同様に、図2及び図
3とは逆の構造に積層することも可能である。Incidentally, it is also possible to have a structure opposite to that of FIG. 1, that is, the conductive layer 2b, the interface layer 4, the organic light emitting layer 3 and the conductive layer 2a are laminated in this order on the substrate, and at least as described above. It is also possible to provide the organic electroluminescent element of the present invention between two substrates, one of which is highly transparent. Similarly, it is also possible to stack in a structure opposite to that of FIGS.
【0035】[0035]
【実施例】次に、本発明を実施例によって更に具体的に
説明するが、本発明はその要旨を越えない限り、以下の
実施例により限定されるものではない。 実施例1及び1' 図2に示す構造を有する有機電界発光素子を以下の方法
で作製した。EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Examples 1 and 1 ′ Organic electroluminescent devices having the structure shown in FIG. 2 were produced by the following method.
【0036】ガラス基板上にインジウム・スズ酸化物
(ITO)透明導電膜を120nm堆積したものをアセ
トンで超音波洗浄、純水で水洗、イソプロピルアルコー
ルで超音波洗浄、乾燥窒素で乾燥、UV/オゾン洗浄を
行った後、真空蒸着装置内に設置して、装置内の真空度
が2×10-6Torr以下になるまで油拡散ポンプを用
いて排気した。A glass substrate on which a transparent conductive film of indium tin oxide (ITO) is deposited to a thickness of 120 nm is ultrasonically washed with acetone, washed with pure water, ultrasonically washed with isopropyl alcohol, dried with dry nitrogen, and UV / ozone. After the cleaning, it was installed in a vacuum vapor deposition apparatus and evacuated using an oil diffusion pump until the degree of vacuum in the apparatus became 2 × 10 −6 Torr or less.
【0037】有機正孔輸送層材料として、以下の構造式
(H1)に示すN,N’−ジフェニル−N,N’−(3
−メチルフェニル)−1,1’−ビフェニル−4,4’
−ジアミンAs the organic hole transport layer material, N, N'-diphenyl-N, N '-(3 represented by the following structural formula (H1) is used.
-Methylphenyl) -1,1'-biphenyl-4,4 '
-Diamine
【0038】[0038]
【化5】 [Chemical 5]
【0039】をセラミックるつぼに入れ、るつぼの周囲
のタンタル線ヒーターで加熱して蒸着を行った。この時
のるつぼの温度は、160〜170℃の範囲で制御し
た。蒸着時の真空度は2×10-6Torrで、蒸着時間
3分20秒で膜厚60nmの有機正孔輸送層3aを得
た。次に、有機電子輸送層3bの材料として、以下の構
造式(E1)に示すアルミニウムの8−ヒドロキシキノ
リン錯体Al(C9H6NO)3 [0039] was placed in a ceramic crucible and heated by a tantalum wire heater around the crucible for vapor deposition. The temperature of the crucible at this time was controlled in the range of 160 to 170 ° C. The degree of vacuum during vapor deposition was 2 × 10 −6 Torr, and an organic hole transport layer 3a having a film thickness of 60 nm was obtained with a vapor deposition time of 3 minutes and 20 seconds. Then, as the material of the organic electron-transporting layer 3b, the aluminum shown in the following structural formulas (E1) 8- hydroxyquinoline complex Al (C 9 H 6 NO) 3
【0040】[0040]
【化6】 [Chemical 6]
【0041】を上記有機正孔輸送層3aの上に同様にし
て蒸着を行なった。この時のるつぼの温度は230〜2
70℃の範囲で制御した。蒸着時の真空度は2×10-6
Torr、蒸着時間は3分30秒、膜厚は75nmであ
った。この層は発光層としての役割を果たす。次に、界
面層4として、先に示した有機シリコン化合物(1)を
有機電子輸送性発光層3bの上に、有機正孔輸送層3a
と同様にして蒸着を行った。蒸着時の真空度は1×10
-6Torr、蒸着時間は30秒、膜厚は5nmであっ
た。The above was vapor-deposited on the organic hole transport layer 3a in the same manner. The temperature of the crucible at this time is 230-2
The temperature was controlled in the range of 70 ° C. The degree of vacuum during vapor deposition is 2 × 10 -6
Torr, vapor deposition time was 3 minutes and 30 seconds, and film thickness was 75 nm. This layer serves as a light emitting layer. Next, as the interface layer 4, the above-mentioned organosilicon compound (1) is formed on the organic electron-transporting light-emitting layer 3b and the organic hole-transporting layer 3a.
Vapor deposition was performed in the same manner as in. The degree of vacuum during vapor deposition is 1 x 10
-6 Torr, vapor deposition time was 30 seconds, and film thickness was 5 nm.
【0042】最後に陰極として、マグネシウムと銀の合
金電極を2元同時蒸着法によって膜厚150nmで蒸着
した。蒸着はモリブデンボートを用いて、真空度は3×
10 -6Torr、蒸着時間は4分30秒で光沢のある膜
が得られた。マグネシウムと銀の原子比は10:1.5
であった(実施例1)。さらに有機シリコン化合物
(1)を用いて、界面層4の膜厚を10nmとしたこと
以外は上記と同様にして素子を作製した(実施例
1')。Finally, as a cathode, a combination of magnesium and silver
Gold electrode is vapor-deposited with a film thickness of 150 nm by the two-source simultaneous vapor deposition method.
did. Vapor deposition uses a molybdenum boat and the degree of vacuum is 3 ×
10 -6Torr, vapor deposition time is 4 minutes and 30 seconds, and it is a glossy film.
was gotten. The atomic ratio of magnesium to silver is 10: 1.5.
(Example 1). Further organosilicon compounds
Using (1), the film thickness of the interface layer 4 was set to 10 nm.
An element was manufactured in the same manner as described above except for (Example
1 ').
【0043】この様にして作製した有機電界発光素子の
ITO電極(陽極)にプラス、マグネシウム・銀合金電
極(陰極)にマイナスの直流電圧を印加してすると、こ
の素子は一様な黄緑色の発光を示し、発光のピーク波長
は560nmであった。作製直後及び真空中で長期間保
存した後の発光特性の結果を表−1に示す。安定した発
光特性がそれぞれ得られた。When a positive DC voltage was applied to the ITO electrode (anode) of the organic electroluminescent element thus manufactured and a negative DC voltage was applied to the magnesium-silver alloy electrode (cathode) of this element, the element was of uniform yellow-green color. It emitted light and had a peak wavelength of 560 nm. Table 1 shows the results of the light emission characteristics immediately after production and after storage in vacuum for a long time. Stable emission characteristics were obtained respectively.
【0044】比較例1 界面層4を設けなかったこと以外は実施例1と同様にし
て、図2に示す構造の有機電界発光素子を作製した。こ
の素子の作製後と真空中保存後の発光特性の測定結果を
表−1に示す。発光輝度及び効率の低下と、駆動電圧の
上昇がみられた。Comparative Example 1 An organic electroluminescent device having the structure shown in FIG. 2 was prepared in the same manner as in Example 1 except that the interface layer 4 was not provided. Table 1 shows the measurement results of the emission characteristics of this device after it was manufactured and after it was stored in vacuum. The emission brightness and efficiency decreased, and the driving voltage increased.
【0045】実施例2 界面層4として、先に示した有機シリコン化合物(1)
と有機シリコン化合物(2)を7:3(重量比)の比率
で混合した膜を5nm設けたこと以外は実施例1と同様
にして、図2に示す構造の有機電界発光素子を作製し
た。この素子の作製後と真空中保存後の発光特性の測定
結果を表−1に示す。安定した発光特性が得られた。Example 2 As the interface layer 4, the above-mentioned organosilicon compound (1) was used.
An organic electroluminescent device having a structure shown in FIG. 2 was produced in the same manner as in Example 1 except that a film having a thickness of 5 nm in which the organic silicon compound (2) and the organic silicon compound (2) were mixed at a ratio of 7: 3 (weight ratio) was provided. Table 1 shows the measurement results of the emission characteristics of this device after it was manufactured and after it was stored in vacuum. Stable light emission characteristics were obtained.
【0046】[0046]
【表2】 [Table 2]
【0047】実施例3 界面層4として、先に示した有機シリコン化合物(4)
を15nmの膜厚で設けたこと以外は実施例1と同様に
して、図2に示す構造の有機電界発光素子を作製した。
この素子を真空中で119日間保存した後、素子からの
発光をCCDカメラを用いて撮影し、画像解析によりダ
ークスポットの面積を測定したところ13%であった。Example 3 As the interface layer 4, the above-mentioned organosilicon compound (4) was used.
An organic electroluminescent device having the structure shown in FIG. 2 was produced in the same manner as in Example 1 except that the film having a thickness of 15 nm was provided.
After this device was stored in a vacuum for 119 days, the light emission from the device was photographed with a CCD camera, and the area of the dark spot was measured by image analysis and found to be 13%.
【0048】比較例2 比較例1と同様にして作製した素子を真空中に80日間
保存した後、実施例3と同様にしてダークスポットの面
積を測定したところ53%であった。 実施例4 有機正孔輸送層3aとして以下の構造式(H2)に示す
キナクリドン化合物Comparative Example 2 The element prepared in the same manner as in Comparative Example 1 was stored in vacuum for 80 days, and then the dark spot area was measured in the same manner as in Example 3 to find that it was 53%. Example 4 A quinacridone compound represented by the following structural formula (H2) as the organic hole transport layer 3a
【0049】[0049]
【化7】 [Chemical 7]
【0050】を、界面層4として先に示した有機シリコ
ン化合物(4)を15nmの膜厚で設けたこと以外は実
施例1と同様にして、図2に示す構造の有機電界発光素
子を作製した。この素子を真空中で100℃、1時間加
熱処理した後の輝度−電圧特性を加熱処理前の特性とと
もに図4に示す。加熱処理することにより駆動電圧は加
熱処理する前より低下させることができた。An organic electroluminescent device having the structure shown in FIG. 2 was prepared in the same manner as in Example 1 except that the organic silicon compound (4) shown above was provided as the interface layer 4 in a thickness of 15 nm. did. FIG. 4 shows the luminance-voltage characteristics after heat-treating this device in vacuum at 100 ° C. for 1 hour together with the characteristics before heat-treatment. By the heat treatment, the driving voltage could be lowered as compared to before the heat treatment.
【0051】比較例3 比較例1と同様にして作製した素子を、実施例4と同様
にして加熱処理した後の輝度−電圧特性を加熱処理前の
特性とともに図5に示す。加熱処理することにより駆動
電圧は加熱処理する前より高電圧側にシフトした。 実施例5 ガラス基板上に、表−1に示した有機シリコン化合物
(1)を膜厚100nmで蒸着した後、実施例1と同様
にして、マグネシウムと銀の合金電極を2元同時蒸着法
によって膜厚150nmで、2mm×20mmの短冊型
に密着マスクを用いて蒸着した。スコッチテープを用い
て上記電極の剥離試験を行ったところ、電極とともに有
機シリコン化合物の薄膜もガラス基板から剥離し、上記
金属電極との付着力は良好であった。Comparative Example 3 An element manufactured in the same manner as in Comparative Example 1 is heat-treated in the same manner as in Example 4, and the luminance-voltage characteristics thereof are shown in FIG. By the heat treatment, the driving voltage was shifted to a higher voltage side than before the heat treatment. Example 5 After depositing the organosilicon compound (1) shown in Table 1 in a film thickness of 100 nm on a glass substrate, a magnesium-silver alloy electrode was formed by a binary simultaneous vapor deposition method in the same manner as in Example 1. It vapor-deposited in a 2 mm x 20 mm strip shape with a film thickness of 150 nm using a contact mask. When a peeling test of the electrode was conducted using a Scotch tape, the thin film of the organic silicon compound was peeled from the glass substrate together with the electrode, and the adhesive force with the metal electrode was good.
【0052】比較例4 有機シリコン化合物(1)の代わりに、前記アルミニウ
ム8−ヒドロキシキノリン錯体(E1)を用いたこと以
外は実施例5と同様にして電極剥離試験用の試料を作製
した。スコッチテープを用いて上記電極の剥離試験を行
ったところ、電極は有機層との間で剥離し付着力は不良
であった。Comparative Example 4 A sample for an electrode peeling test was prepared in the same manner as in Example 5 except that the aluminum 8-hydroxyquinoline complex (E1) was used instead of the organosilicon compound (1). When a peeling test of the above electrode was conducted using Scotch tape, the electrode peeled from the organic layer and the adhesion was poor.
【0053】[0053]
【発明の効果】本発明の有機電界発光素子は、陽極、有
機発光層、陰極が基板上に順次設けられ、有機発光層と
陰極の間に特定の化合物を含有する界面層が設けられて
いるため、両導電層を電極として電圧を印加した場合、
長期に渡り、安定した発光特性を得ることができる。In the organic electroluminescent device of the present invention, an anode, an organic light emitting layer and a cathode are sequentially provided on a substrate, and an interface layer containing a specific compound is provided between the organic light emitting layer and the cathode. Therefore, when voltage is applied with both conductive layers as electrodes,
Stable light emission characteristics can be obtained over a long period of time.
【0054】従って、本発明の電界発光素子はフラット
パネル・ディスプレイ(例えばOAコンピュータ用や壁
掛けテレビ)の分野や面発光体としての特徴を生かした
光源(例えば、複写機の光源、液晶ディスプレイや計器
類のバックライト光源)、表示板、標識灯への応用が考
えられ、その技術的価値は非常に大きい。Therefore, the electroluminescent device of the present invention is used in the field of flat panel displays (for example, for OA computers and wall-mounted televisions) and light sources (for example, light sources for copiers, liquid crystal displays and instruments) that make the most of the characteristics as a surface light emitter. It can be applied to various types of backlight sources, display boards, and marker lights, and its technical value is extremely large.
【図1】本発明の有機電界発光素子の一実施例を示した
模式断面図。FIG. 1 is a schematic cross-sectional view showing an example of an organic electroluminescence device of the present invention.
【図2】本発明の有機電界発光素子の別の実施例を示し
た模式断面図。FIG. 2 is a schematic cross-sectional view showing another embodiment of the organic electroluminescent element of the present invention.
【図3】本発明の有機電界発光素子のその他の実施例を
示した模式断面図。FIG. 3 is a schematic cross-sectional view showing another embodiment of the organic electroluminescent element of the present invention.
【図4】本発明の実施例4で作製した有機電界発光素子
の発光輝度−電圧特性の加熱処理による変化を表す図。FIG. 4 is a diagram showing changes in light emission luminance-voltage characteristics of an organic electroluminescence device manufactured in Example 4 of the present invention due to heat treatment.
【図5】本発明の比較例3で作製した有機電界発光素子
の発光輝度−電圧特性の加熱処理による変化を表す図。FIG. 5 is a diagram showing changes in light emission luminance-voltage characteristics of an organic electroluminescence device manufactured in Comparative Example 3 of the present invention due to heat treatment.
1 基板 2a、2b 導電層 3 有機発光層 3a 正孔輸送層 3b 有機電子輸送層 3c 3bとは異なる化合物で構成される有機電子輸送
層 4 界面層DESCRIPTION OF SYMBOLS 1 Substrate 2a, 2b Conductive layer 3 Organic light emitting layer 3a Hole transport layer 3b Organic electron transport layer 3c Organic electron transport layer composed of a compound different from 3b 4 Interface layer
Claims (1)
有機電界発光素子であって、有機発光層と陰極との間に
有機シリコン化合物を含有する界面層を設けたことを特
徴とする有機電界発光素子。1. An organic electroluminescent device in which an anode, an organic light emitting layer, and a cathode are sequentially stacked, wherein an organic electroluminescent device-containing interface layer is provided between the organic light emitting layer and the cathode. Electroluminescent device.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5116206A JPH06325871A (en) | 1993-05-18 | 1993-05-18 | Organic electroluminescent element |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5116206A JPH06325871A (en) | 1993-05-18 | 1993-05-18 | Organic electroluminescent element |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06325871A true JPH06325871A (en) | 1994-11-25 |
Family
ID=14681473
Family Applications (1)
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JP5116206A Pending JPH06325871A (en) | 1993-05-18 | 1993-05-18 | Organic electroluminescent element |
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JP (1) | JPH06325871A (en) |
Cited By (56)
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-
1993
- 1993-05-18 JP JP5116206A patent/JPH06325871A/en active Pending
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