JP2001043973A - Organic luminescent element and manufacture of the same - Google Patents
Organic luminescent element and manufacture of the sameInfo
- Publication number
- JP2001043973A JP2001043973A JP11214712A JP21471299A JP2001043973A JP 2001043973 A JP2001043973 A JP 2001043973A JP 11214712 A JP11214712 A JP 11214712A JP 21471299 A JP21471299 A JP 21471299A JP 2001043973 A JP2001043973 A JP 2001043973A
- Authority
- JP
- Japan
- Prior art keywords
- organic light
- layer
- organic
- light emitting
- emitting device
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 124
- 238000002347 injection Methods 0.000 claims abstract description 117
- 239000007924 injection Substances 0.000 claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 28
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 28
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 247
- 239000012044 organic layer Substances 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 41
- -1 metal complex compound Chemical class 0.000 claims description 40
- 230000002950 deficient Effects 0.000 claims description 39
- 229910052783 alkali metal Inorganic materials 0.000 claims description 27
- 150000001340 alkali metals Chemical class 0.000 claims description 27
- HQQKMOJOCZFMSV-UHFFFAOYSA-N dilithium phthalocyanine Chemical compound [Li+].[Li+].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HQQKMOJOCZFMSV-UHFFFAOYSA-N 0.000 claims description 21
- 230000005525 hole transport Effects 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- RLDWIFDMZUBMGW-UHFFFAOYSA-N 29h,31h-phthalocyanine, disodium salt Chemical compound [Na+].[Na+].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 RLDWIFDMZUBMGW-UHFFFAOYSA-N 0.000 claims description 11
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims 2
- 150000004696 coordination complex Chemical class 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000010549 co-Evaporation Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 4
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XZCJVWCMJYNSQO-UHFFFAOYSA-N butyl pbd Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 XZCJVWCMJYNSQO-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000990 laser dye Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- VJDRTBUXSHGISI-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[K] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[K] VJDRTBUXSHGISI-UHFFFAOYSA-N 0.000 description 1
- RTQNANWOIGGKNJ-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Na].[Na] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Na].[Na] RTQNANWOIGGKNJ-UHFFFAOYSA-N 0.000 description 1
- DWJFGGVNPNGBBN-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=NC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=NC=C1 DWJFGGVNPNGBBN-UHFFFAOYSA-N 0.000 description 1
- 241001377010 Pila Species 0.000 description 1
- DSGYQDCLQRIYNW-UHFFFAOYSA-N [Li].[Li].c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3 Chemical compound [Li].[Li].c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3 DSGYQDCLQRIYNW-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- RWASOQSEFLDYLC-UHFFFAOYSA-N beryllium dihydride Chemical compound [BeH2] RWASOQSEFLDYLC-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- DNZSHSJERXNJGX-UHFFFAOYSA-N chembl3040240 Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CN=CC=2)C=2C=CC(N=2)=C(C=2C=CN=CC=2)C2=CC=C3N2)C=2C=CN=CC=2)=NC1=C3C1=CC=NC=C1 DNZSHSJERXNJGX-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- DCZNSJVFOQPSRV-UHFFFAOYSA-N n,n-diphenyl-4-[4-(n-phenylanilino)phenyl]aniline Chemical class C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 DCZNSJVFOQPSRV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical class N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- VEPOUCHBIJXQFI-UHFFFAOYSA-N pyrazabole Chemical compound [B-]1N2C=CC=[N+]2[B-][N+]2=CC=CN12 VEPOUCHBIJXQFI-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- 239000013638 trimer Substances 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、発光ディスプレイ
や液晶ディスプレイ用バックライト等として用いられる
表示素子に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display element used as a light emitting display or a backlight for a liquid crystal display.
【０００２】[0002]
【従来の技術】エレクトロルミネッセンス（ＥＬ）パネ
ルは視認性が高く、表示能力に優れ、高速応答も可能と
いう特徴を持っている。近年、有機化合物を構成材料と
する有機発光素子について報告がなされた（例えば、Ap
plied Physics Letters,51,1987,P.913.）。この報告に
は有機発光層及びホール輸送層を積層した構造の有機発
光素子が記載されており、今日に至るまで、この基本構
成に基づいて研究開発が進められている。図１に有機発
光素子の基本構成を示す。2. Description of the Related Art Electroluminescent (EL) panels have high visibility, excellent display capability, and high-speed response. In recent years, reports have been made on organic light-emitting devices using an organic compound as a constituent material (for example, Ap
plied Physics Letters, 51, 1987, P.913.). This report describes an organic light-emitting device having a structure in which an organic light-emitting layer and a hole transport layer are stacked, and to date, research and development have been carried out based on this basic configuration. FIG. 1 shows a basic configuration of an organic light emitting device.
【０００３】図１中、１はガラス基板、２は透明電極、
３は陰極、５は電子輸送性発光層、６はホール輸送層を
それぞれ表している。有機発光素子の別の構成として
は、５の電子輸送性発光層を電子輸送層と、有機発光層
とに機能分離する場合もある。In FIG. 1, 1 is a glass substrate, 2 is a transparent electrode,
Reference numeral 3 denotes a cathode, 5 denotes an electron transporting light emitting layer, and 6 denotes a hole transporting layer. As another configuration of the organic light emitting device, the electron transporting light emitting layer of No. 5 may be functionally separated into an electron transporting layer and an organic light emitting layer.
【０００４】陰極３は、低仕事関数であるアルカリ金属
やアルカリ土類金属と、アルミニウム、銀などの安定な
金属との合金を形成することにより、安定でかつ電子注
入が容易な陰極が用いられている。例えば、特開平５−
１２１１７２号公報において、合金に含まれるＬｉ濃度
を０．０１ｗｔ％以上０．１ｗｔ％以下という微少な量
に制御することにより発光効率が高くかつ環境安定性の
高いＥＬ素子を実現している。他の方法としては、金属
電極を積層構成にする場合もあり、電子注入電極として
有機層側に低仕事関数の金属薄膜を成膜し、この上に保
護電極として安定な金属からなる電極膜を成膜すること
で、水分等に対して反応性の高いアルカリ金属やアルカ
リ土類金属を保護しながら電子注入性を維持する方法も
ある。これによって、Ｌｉ等を低濃度で制御する必要も
なく、簡便なプロセスで作製可能となる。The cathode 3 is made of an alloy of a low work function alkali metal or alkaline earth metal and a stable metal such as aluminum or silver, so that a stable and easy electron injection cathode is used. ing. For example, Japanese Patent Application Laid-Open
In Japanese Patent No. 121172, an EL element having high luminous efficiency and high environmental stability is realized by controlling the concentration of Li contained in an alloy to a minute amount of 0.01 wt% to 0.1 wt%. As another method, a metal electrode may be formed in a laminated structure.A metal thin film having a low work function is formed on the organic layer side as an electron injection electrode, and an electrode film made of a stable metal is formed thereon as a protective electrode. There is also a method in which an electron injection property is maintained while forming a film to protect an alkali metal or an alkaline earth metal highly reactive to moisture or the like. Thus, it is not necessary to control Li and the like at a low concentration, and it is possible to manufacture the device by a simple process.
【０００５】さらに近年においては、図２のように図１
の構成に電子注入層４を積層する場合もある。In recent years, as shown in FIG.
In some cases, the electron injection layer 4 is laminated on the above structure.
【０００６】例えば、特開平９−１７５７４号公報にお
いて、電子注入層材料にアルカリ金属化合物を使用し、
膜厚を最適化することにより、特性の再現性が高く、低
印加電圧で高輝度発光が可能な有機ＥＬ素子を得られる
と記載されている。また、これら絶縁物質からなる電子
注入層の膜厚に関しては、ダークスポットとの関連等に
ついて詳細に報告されている [T.Wakimoto,Y.Fukuda,
K.Nagayama,A.Yokoi,H.Nakada and M.Tsuchida,IEEE Tr
ansactions on Electron Devices,Vol.44,No.8,p1245,1
997］。For example, in Japanese Patent Application Laid-Open No. 9-17574, an alkali metal compound is used as a material for an electron injection layer,
It is described that by optimizing the film thickness, an organic EL element having high reproducibility of characteristics and capable of emitting light with high luminance at a low applied voltage can be obtained. The thickness of the electron injection layer made of these insulating materials has been reported in detail in relation to dark spots, etc. [T. Wakimoto, Y. Fukuda,
K. Nagayama, A. Yokoi, H. Nakada and M. Tsuchida, IEEE Tr
ansactions on Electron Devices, Vol.44, No.8, p1245,1
997].
【０００７】このように、有機発光素子の開発におい
て、電子注入層は発光効率や寿命を決定する重要な要素
として取り組まれている。As described above, in the development of the organic light emitting device, the electron injection layer has been addressed as an important factor for determining the luminous efficiency and the lifetime.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、電子注
入特性に優れたアルカリ金属やアルカリ土類金属は、反
応性に富むため酸化物や窒化物を形成しやすいため作業
性が悪く、蒸着過程における真空下であっても、蒸着ボ
ート内に設置している間あるいは蒸着中の基板に付着す
るまでの間あるいは基板に付着した後安定な金属電極で
被覆されるまでの間において酸化や窒化の作用を受けや
すい。However, alkali metals and alkaline earth metals having excellent electron injecting properties are poor in workability because they are easy to form oxides and nitrides because of their high reactivity, and the vacuum in the vapor deposition process is poor. Even underneath, the oxidizing and nitriding effects may occur during installation in a deposition boat, or until it adheres to the substrate being deposited, or until it is covered with a stable metal electrode after being attached to the substrate. Easy to receive.
【０００９】さらに、アルカリ金属やアルカリ土類金属
の無機化合物からなる電子注入層は、作業性、再現性の
点において優れている一方で、発光輝度や寿命の点にお
いては突出して改善されていない。特に有機発光素子の
劣化要因の一つがアルカリ金属やアルカリ土類金属のよ
うな反応性の高い金属の変質にあるため、これらを安定
な無機化合物に置き換えて適用したものの、デバイスの
寿命特性は改善されていないという課題があった。Further, an electron injection layer made of an inorganic compound of an alkali metal or an alkaline earth metal is excellent in workability and reproducibility, but is not remarkably improved in light emission luminance and life. . In particular, one of the causes of deterioration of organic light-emitting elements is the deterioration of highly reactive metals such as alkali metals and alkaline earth metals, and these were replaced with stable inorganic compounds, but the device life characteristics were improved. There was a problem that was not done.
【００１０】[0010]
【課題を解決するための手段】そこで我々は、低仕事関
数の金属を含む有機金属錯化合物を電子注入材料として
用いることにより、あるいは電子不足化合物を電子注入
材料として用いることにより、有機発光素子の高輝度発
光、高再現性を維持しながら、長寿命化を実現するに至
った。同時に、特性の優れた有機発光素子を定常的に得
られる製造方法も見出した。Accordingly, we have developed an organic light-emitting device by using an organometallic complex compound containing a metal with a low work function as an electron injecting material or using an electron deficient compound as an electron injecting material. This has resulted in a longer life while maintaining high luminance emission and high reproducibility. At the same time, the inventors have found a manufacturing method capable of constantly obtaining an organic light emitting device having excellent characteristics.
【００１１】具体的には、本願の請求項１の発明によれ
ば、陽極および陰極間に、少なくとも有機発光層と有機
電子注入層を有する有機発光素子において、前記有機電
子注入層がアルカリ金属またはアルカリ土類金属を中心
金属に持つ有機金属錯化合物を含むことを特徴とする有
機発光素子が提供される。Specifically, according to the invention of claim 1 of the present application, in an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer is made of an alkali metal or There is provided an organic light emitting device comprising an organometallic complex compound having an alkaline earth metal as a central metal.
【００１２】本願の請求項２の発明によれば、陽極およ
び陰極間に、少なくとも有機発光層と有機電子注入層を
有する有機発光素子において、前記有機電子注入層が下
記一般式（化４）を含むことを特徴とする有機発光素子
が提供される。According to the invention of claim 2 of the present application, in an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer has the following general formula (Formula 4) An organic light emitting device characterized by comprising:
【００１３】[0013]
【化４】 Embedded image
【００１４】（Ｒ１〜Ｒ１２はそれぞれ水素、炭素数１
〜６のアルキル基、ハロゲン、炭素数６〜１８のアリー
ル基、窒素原子を１〜３個含む複素芳香環、ビニル基、
アミノ基、シアノ基またはチオール基を示し、Ｒ１〜Ｒ
１２は互いに同一であっても異なっていてもよく、Ｒ１
とＲ２，Ｒ４とＲ５，Ｒ７とＲ８，Ｒ１０とＲ１１は互
いに結合して飽和あるいは不飽和の５員環または６員環
を形成してもよく、縮合多環芳香族を形成してもよい。
Ｍはアルカリ金属またはアルカリ土類金属）。(R1 to R12 each represent hydrogen, carbon number 1
Alkyl groups, halogens, aryl groups having 6 to 18 carbon atoms, heteroaromatic rings containing 1 to 3 nitrogen atoms, vinyl groups,
An amino group, a cyano group or a thiol group;
12 may be the same or different from each other;
And R2, R4 and R5, R7 and R8, R10 and R11 may combine with each other to form a saturated or unsaturated 5- or 6-membered ring, or may form a condensed polycyclic aromatic.
M is an alkali metal or an alkaline earth metal).
【００１５】本願の請求項３は、請求項２記載の有機電
子注入層がジリチウムフタロシアニンを含むとしたもの
である。According to a third aspect of the present invention, the organic electron injection layer according to the second aspect includes dilithium phthalocyanine.
【００１６】本願の請求項４は、請求項２記載の有機電
子注入層がジソディウムフタロシアニンを含むとしたも
のである。According to claim 4 of the present application, the organic electron injection layer according to claim 2 contains disodium phthalocyanine.
【００１７】本願の請求項５の発明によれば、陽極およ
び陰極間に、少なくとも有機発光層と有機電子注入層を
有する有機発光素子において、前記有機電子注入層が下
記一般式（化５）を含むことを特徴とする有機発光素子
が提供される。According to the invention of claim 5 of the present application, in an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer has the following general formula (Formula 5) An organic light emitting device characterized by comprising:
【００１８】[0018]
【化５】 Embedded image
【００１９】（Ｒ１〜Ｒ１２はそれぞれ水素、炭素数１
〜６のアルキル基、ハロゲン、炭素数６〜１８のアリー
ル基、窒素原子を１〜３個含む複素芳香環、ビニル基、
アミノ基、シアノ基またはチオール基を示し、Ｒ１〜Ｒ
１２は互いに同一であっても異なっていてもよく、Ｒ１
とＲ２，Ｒ４とＲ５，Ｒ７とＲ８，Ｒ１０とＲ１１は互
いに結合して飽和あるいは不飽和の５員環または６員環
を形成してもよく、縮合多環芳香族を形成してもよい。
Ｍはアルカリ金属またはアルカリ土類金属）。(R1 to R12 each represent hydrogen, carbon number 1
Alkyl groups, halogens, aryl groups having 6 to 18 carbon atoms, heteroaromatic rings containing 1 to 3 nitrogen atoms, vinyl groups,
An amino group, a cyano group or a thiol group;
12 may be the same or different from each other;
And R2, R4 and R5, R7 and R8, R10 and R11 may combine with each other to form a saturated or unsaturated 5- or 6-membered ring, or may form a condensed polycyclic aromatic.
M is an alkali metal or an alkaline earth metal).
【００２０】本願の請求項６の発明によれば、陽極およ
び陰極間に、少なくとも有機発光層と有機電子注入層を
有する有機発光素子において、前記有機電子注入層が電
子不足化合物を含むことを特徴とする有機発光素子が提
供される。According to the invention of claim 6 of the present application, in an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer contains an electron deficient compound. Is provided.
【００２１】本願の請求項７は、請求項６記載の電子不
足化合物が下記一般式（化６）であるとしたものであ
る。According to claim 7 of the present application, the electron-deficient compound according to claim 6 has the following general formula (Formula 6).
【００２２】[0022]
【化６】 Embedded image
【００２３】（Ｒ１及びＲ２は少なくとも２つの窒素原
子を含む含窒素芳香環もしくは含窒素芳香環誘導体を有
する架橋配位子あるいはハロゲン、炭素数１〜３のアル
キルを有する架橋配位子であり、含窒素芳香環中の窒素
を配位原子とする。Ｒ３，Ｒ４，Ｒ５およびＲ６はそれ
ぞれ水素、アルキル、アリール、アリール誘導体及び少
なくとも１つの窒素原子を含む含窒素芳香環もしくは含
窒素芳香環誘導体から選ばれる１つであり、Ｍは中心金
属）。(R1 and R2 are a bridging ligand having a nitrogen-containing aromatic ring or a nitrogen-containing aromatic ring derivative containing at least two nitrogen atoms or a bridging ligand having a halogen or an alkyl having 1 to 3 carbon atoms, R 3, R 4, R 5 and R 6 are each a hydrogen, an alkyl, an aryl or an aryl derivative and a nitrogen-containing aromatic ring or a nitrogen-containing aromatic ring derivative containing at least one nitrogen atom. (M is the central metal).
【００２４】本願の請求項８は、請求項６記載の電子不
足化合物が、ピラザボール構造を有するとしたものであ
る。According to claim 8 of the present application, the electron-deficient compound according to claim 6 has a pyrazaball structure.
【００２５】本願の請求項９は、請求項６記載の電子不
足化合物が、４，４，８，８−テトラキス（１Ｈ−ピラ
ゾールー１−イル）ピラザボールであるとしたものであ
る。According to a ninth aspect of the present invention, the electron-deficient compound according to the sixth aspect is 4,4,8,8-tetrakis (1H-pyrazol-1-yl) pyrazaball.
【００２６】本願の請求項１０は、請求項１〜９記載の
有機電子注入層の膜厚が０．２〜２ｎｍであるとしたも
のである。According to a tenth aspect of the present invention, the thickness of the organic electron injection layer according to the first to ninth aspects is 0.2 to 2 nm.
【００２７】本願の請求項１１は、請求項１〜１０記載
の陰極及び陽極間の層が有機発光層からなるとしたもの
である。According to claim 11 of the present application, the layer between the cathode and the anode according to claims 1 to 10 comprises an organic light emitting layer.
【００２８】本願の請求項１２は、請求項１〜１０記載
の陰極及び陽極間の層がホール輸送層と有機発光層の積
層構成であるとしたものである。According to a twelfth aspect of the present invention, the layer between the cathode and the anode according to the first to tenth aspects has a laminated structure of a hole transport layer and an organic light emitting layer.
【００２９】本願の請求項１３は、請求項１〜１０記載
の陰極及び陽極間の層が有機発光層と電子輸送層の積層
構成であるとしたものである。A thirteenth aspect of the present invention is the one according to the first to tenth aspects, wherein the layer between the cathode and the anode has a laminated structure of an organic light emitting layer and an electron transport layer.
【００３０】本願の請求項１４は、請求項１〜１０記載
の陰極及び陽極間の層がホール輸送層と有機発光層と電
子輸送層の積層構成であるとしたものである。According to a fourteenth aspect of the present invention, the layer between the cathode and the anode according to the first to tenth aspects has a laminated structure of a hole transport layer, an organic light emitting layer, and an electron transport layer.
【００３１】本願の請求項１５の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層にアルカリ金属またはアルカリ土
類金属を中心金属に持つ有機金属錯化合物からなる電子
注入化合物を含むことを特徴とする有機発光素子が提供
される。According to the fifteenth aspect of the present invention, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, an organic metal complex compound having an alkali metal or an alkaline earth metal as a central metal in the organic layer An organic light emitting device comprising an electron injection compound comprising:
【００３２】本願の請求項１６の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層に一般式（化４）からなる電子注
入化合物を含むことを特徴とする有機発光素子が提供さ
れる。According to the invention of claim 16 of the present application, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, the organic layer contains an electron injection compound represented by the general formula (Formula 4). Is provided.
【００３３】本願の請求項１７は、請求項１６記載の電
子注入化合物がジリチウムフタロシアニンであるとした
ものである。According to claim 17 of the present application, the electron injecting compound according to claim 16 is dilithium phthalocyanine.
【００３４】本願の請求項１８は、請求項１６記載の電
子注入化合物がジソディウムフタロシアニンであるとし
たものである。According to claim 18 of the present application, the electron injecting compound according to claim 16 is disodium phthalocyanine.
【００３５】本願の請求項１９の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層に一般式（化５）からなる電子注
入化合物を含むことを特徴とする有機発光素子が提供さ
れる。According to a nineteenth aspect of the present invention, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, the organic layer contains an electron injection compound represented by the general formula (Formula 5). Is provided.
【００３６】本願の請求項２０の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層に電子不足化合物からなる電子注
入化合物を含むことを特徴とする有機発光素子。According to the twentieth aspect of the present invention, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, the organic layer contains an electron injection compound comprising an electron deficient compound. Light emitting element.
【００３７】本願の請求項２１は、請求項２０記載の電
子不足化合物が一般式（化６）であるとしたものであ
る。According to a twenty-first aspect of the present invention, the electron-deficient compound according to the twentieth aspect has the general formula (Formula 6).
【００３８】本願の請求項２２は、前記電子不足化合物
が、ピラザボール構造を有するとしたものである。According to claim 22 of the present application, the electron-deficient compound has a pyrazaball structure.
【００３９】本願の請求項２３は、請求項２０記載の電
子不足化合物が、４，４，８，８−テトラキス（１Ｈ−
ピラゾールー１−イル）ピラザボールであるとしたもの
である。According to a twenty-third aspect of the present invention, the electron-deficient compound according to the twentieth aspect is characterized in that the compound is 4,4,8,8-tetrakis (1H-
Pyrazol-1-yl) pyrazaball.
【００４０】本願の請求項２４の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層の陰極側にアルカリ金属またはア
ルカリ土類金属を中心金属に持つ有機金属錯化合物から
なる電子注入化合物を含むことを特徴とする有機発光素
子が提供される。According to the invention of claim 24 of the present application, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, an organic light emitting device having an alkali metal or an alkaline earth metal as a central metal on the cathode side of the organic layer. There is provided an organic light emitting device comprising an electron injection compound comprising a metal complex compound.
【００４１】本願の請求項２５の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層の陰極側に一般式（化４）からな
る電子注入化合物を含むことを特徴とする有機発光素子
が提供される。According to the invention of claim 25 of the present application, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, an electron injecting compound represented by the general formula (Formula 4) is included on the cathode side of the organic layer. An organic light emitting device is provided.
【００４２】本願の請求項２６は、請求項２５記載の電
子注入化合物がジリチウムフタロシアニンであるとした
ものである。According to claim 26 of the present application, the electron injecting compound according to claim 25 is dilithium phthalocyanine.
【００４３】本願の請求項２７は、請求項２５記載の電
子注入化合物がジソディウムフタロシアニンであるとし
たものである。Claim 27 of the present application is that the electron injection compound according to claim 25 is disodium phthalocyanine.
【００４４】本願の請求項２８の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層の陰極側に一般式（化５）からな
る電子注入化合物を含むことを特徴とする有機発光素子
が提供される。According to the twenty-eighth aspect of the present invention, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, an electron injecting compound represented by the general formula (Formula 5) is included on the cathode side of the organic layer. An organic light emitting device is provided.
【００４５】本願の請求項２９の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子において、有機層の陰極側に電子不足化合物からな
る電子注入化合物を含むことを特徴とする有機発光素子
が提供される。According to the invention of claim 29 of the present application, in an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, an electron injecting compound comprising an electron deficient compound is included on the cathode side of the organic layer. Is provided.
【００４６】本願の請求項３０は、請求項２９記載の電
子不足化合物が一般式（化６）であるとしたものであ
る。Claim 30 of the present application is based on the assumption that the electron-deficient compound according to claim 29 has the general formula (Formula 6).
【００４７】本願の請求項３１は、請求項２９記載の電
子不足化合物が、ピラザボール構造を有するとしたもの
である。According to claim 31 of the present application, the electron-deficient compound according to claim 29 has a pyrazaball structure.
【００４８】本願の請求項３２は、請求項２９記載の電
子不足化合物が、４，４，８，８−テトラキス（１Ｈ−
ピラゾールー１−イル）ピラザボールであるとしたもの
である。According to claim 32 of the present application, the electron-deficient compound according to claim 29 is characterized in that the compound is 4,4,8,8-tetrakis (1H-
Pyrazol-1-yl) pyrazaball.
【００４９】本願の請求項３３は、請求項１５〜３２記
載の電子注入化合物を、有機層中または有機層の陰極側
に、均一に含むとしたものである。A thirty-third aspect of the present invention is directed to the electron injection compound according to the fifteenth to thirty-second aspects, wherein the electron injecting compound is uniformly contained in the organic layer or on the cathode side of the organic layer.
【００５０】本願の請求項３４は、請求項１５〜３２記
載の電子注入化合物を、有機層中または有機層の陰極側
に、陰極に近接するほど高濃度になるように濃度勾配を
つけて含むとしたものである。Claim 34 of the present application comprises the electron injecting compound according to any one of claims 15 to 32 in the organic layer or on the cathode side of the organic layer with a concentration gradient such that the concentration becomes higher as approaching the cathode. It is what it was.
【００５１】本願の請求項３５は、請求項１５〜３２記
載の有機層が有機発光層からなるとしたものである。According to claim 35 of the present application, the organic layer according to claims 15 to 32 comprises an organic light emitting layer.
【００５２】本願の請求項３６は、請求項１５〜３２記
載の有機層がホール輸送層と有機発光層の積層構成であ
り、電子注入化合物を含む層が有機発光層であるとした
ものである。Claim 36 of the present application is that the organic layer according to claims 15 to 32 has a laminated structure of a hole transport layer and an organic light emitting layer, and the layer containing the electron injection compound is the organic light emitting layer. .
【００５３】本願の請求項３７は、請求項１５〜３２記
載の有機層が有機発光層と電子輸送層の積層構成であ
り、電子注入化合物を含む層が電子輸送層であるとした
ものである。Claim 37 of the present application is characterized in that the organic layer according to claims 15 to 32 has a laminated structure of an organic light emitting layer and an electron transport layer, and the layer containing an electron injection compound is an electron transport layer. .
【００５４】本願の請求項３８は、請求項１５〜３２記
載の有機層がホール輸送層と有機発光層と電子輸送層の
積層構成であり、電子注入化合物を含む層が電子輸送層
であるとしたものである。According to claim 38 of the present application, the organic layer according to claims 15 to 32 has a laminated structure of a hole transporting layer, an organic light emitting layer and an electron transporting layer, and the layer containing an electron injecting compound is an electron transporting layer. It was done.
【００５５】本願の請求項３９は、請求項１〜３８記載
の陰極が仕事関数４．０ｅＶ以上の金属からなるとした
ものである。In a thirty-ninth aspect of the present invention, the cathode according to the first to thirty-eighth aspects is made of a metal having a work function of 4.0 eV or more.
【００５６】本願の請求項４０は、請求項１〜３８記載
の陰極がＡｌ、Ａｇ、Ｉｎ、Ｂｉのうちのいずれかであ
るとしたものである。According to claim 40 of the present application, the cathode according to claims 1 to 38 is any one of Al, Ag, In, and Bi.
【００５７】本願の請求項４１の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層と有機電子注入層
を有する有機発光素子の製造方法において、前記有機電
子注入層をアルカリ金属またはアルカリ土類金属を中心
金属に持つ有機金属錯化合物から形成する有機発光素子
の製造方法が提供される。According to the invention of claim 41 of the present application, in a method for manufacturing an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer is made of an alkali metal or alkaline earth. Provided is a method for manufacturing an organic light emitting device formed from an organometallic complex compound having a similar metal as a central metal.
【００５８】本願の請求項４２の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層と有機電子注入層
を有する有機発光素子の製造方法において、前記有機電
子注入層を一般式（化４）から形成する有機発光素子の
製造方法が提供される。According to the invention of claim 42 of the present application, in a method of manufacturing an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer has a general formula ) Is provided.
【００５９】本願の請求項４３の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層と有機電子注入層
を有する有機発光素子の製造方法において、前記有機電
子注入層を一般式（化５）から形成する有機発光素子の
製造方法が提供される。According to the invention of claim 43 of the present application, in a method for manufacturing an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer is represented by the general formula ) Is provided.
【００６０】本願の請求項４４の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層と有機電子注入層
を有する有機発光素子の製造方法において、前記有機電
子注入層を電子不足化合物から形成する有機発光素子の
製造方法が提供される。According to the invention of claim 44 of the present application, in a method for manufacturing an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, the organic electron injection layer is formed from an electron deficient compound. A method for manufacturing an organic light emitting device is provided.
【００６１】本願の請求項４５の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子の製造方法において、有機層あるいは有機層の陰極
側にアルカリ金属またはアルカリ土類金属を中心金属に
持つ有機金属錯化合物からなる電子注入化合物を含有さ
せる有機発光素子の製造方法が提供される。According to a forty-fifth aspect of the present invention, in a method of manufacturing an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, an alkali metal or an alkaline earth metal is provided on the organic layer or the cathode side of the organic layer. And a method for producing an organic light-emitting device containing an electron-injecting compound composed of an organometallic complex compound having as a central metal.
【００６２】本願の請求項４６の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子の製造方法において、有機層あるいは有機層の陰極
側に一般式（化４）からなる電子注入化合物を含有させ
る有機発光素子の製造方法が提供される。According to the invention of claim 46 of the present application, in a method of manufacturing an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, the organic layer or the cathode side of the organic layer is represented by the general formula (Formula 4) The present invention provides a method for producing an organic light-emitting device containing the electron injection compound.
【００６３】本願の請求項４７の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子の製造方法において、有機層あるいは有機層の陰極
側に一般式（化５）からなる電子注入化合物を含有させ
る有機発光素子の製造方法が提供される。According to the invention of claim 47 of the present application, in a method for manufacturing an organic light-emitting device having at least an organic light-emitting layer between an anode and a cathode, the organic layer or the cathode side of the organic layer is represented by the general formula (Formula 5) The present invention provides a method for producing an organic light-emitting device containing the electron injection compound.
【００６４】本願の請求項４８の発明によれば、陽極お
よび陰極間に、少なくとも有機発光層を有する有機発光
素子の製造方法において、有機層あるいは有機層の陰極
側に電子不足化合物からなる電子注入化合物を含有させ
る有機発光素子の製造方法が提供される。According to the invention of claim 48 of the present application, in a method of manufacturing an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, an electron injection comprising an electron deficient compound is carried out on the organic layer or on the cathode side of the organic layer. A method for manufacturing an organic light emitting device containing a compound is provided.
【００６５】[0065]
【発明の実施の形態】以下本発明の実施の形態について
説明する。Embodiments of the present invention will be described below.
【００６６】本発明の有機発光素子は基本構成として、
透明基板上に陽極と陰極と少なくとも陽極と陰極の間に
設けられた有機発光層により構成されるが、前述したよ
うにホール輸送層、電子輸送層等と積層構成を用いるこ
とができる。The organic light emitting device of the present invention has a basic structure
It is composed of an anode and a cathode and at least an organic light emitting layer provided between the anode and the cathode on the transparent substrate. As described above, a laminated structure with a hole transport layer, an electron transport layer and the like can be used.
【００６７】透明基板は、上述した薄膜を積層した有機
発光素子を担持できるものであれば良く、また、有機層
内で生じた発光を取り出せるように透明ないし半透明の
材料であれば良く、コーニング１７３７等のガラス、あ
るいはポリエステルその他の樹脂フィルム等を用いる。The transparent substrate may be any as long as it can carry the organic light-emitting element having the above-mentioned thin film laminated thereon, and may be any transparent or translucent material so as to extract the luminescence generated in the organic layer. Glass such as 1737 or polyester or other resin film is used.
【００６８】一般に有機発光素子は、少なくとも一方の
電極を透明ないし半透明にすることにより、面発光を取
り出すことが可能となる。通常、正孔注入電極としての
陽極にはＩＴＯ（インジウム錫酸化物）膜を用いること
が多い。他に、酸化錫、Ｎｉ，Ａｕ，Ｐｔ，Ｐｄ等が挙
げられる。ＩＴＯ膜はその透明性を向上させ、あるいは
抵抗率を低下させる目的で、スパッタ、エレクトロンビ
ーム蒸着、イオンプレーティング等の成膜方法が採用さ
れている。また、膜厚は必要とされるシート抵抗値と可
視光透過率から決定されるが、有機発光素子では比較的
駆動電流密度が高いため、シート抵抗値を小さくするた
め１００ｎｍ以上の厚さで用いられることが多い。In general, an organic light emitting element can emit surface light by making at least one electrode transparent or translucent. Usually, an ITO (indium tin oxide) film is often used for an anode serving as a hole injection electrode. Other examples include tin oxide, Ni, Au, Pt, and Pd. For the purpose of improving the transparency or reducing the resistivity of the ITO film, a film forming method such as sputtering, electron beam evaporation, or ion plating is employed. The film thickness is determined from the required sheet resistance value and visible light transmittance. However, since the organic light emitting element has a relatively high driving current density, it is used in a thickness of 100 nm or more to reduce the sheet resistance value. Is often done.
【００６９】ホール輸送層を構成する材料としては、ト
リフェニルアミンを基本骨格として持つ誘導体が好まし
い。例えば、特開平７−１２６６１５号公報記載のテト
ラフェニルベンジジン化合物、トリフェニルアミン３量
体、ベンジジン２量体が挙げられる。また、特開平８−
４８６５６号公報記載の種々のトリフェニルジアミン誘
導体、あるいは特開平７−６５９５８号公報記載のＭＴ
ＰＤ（通称ＴＰＤ）でもよい。特には、特願平９−３４
１２３８号記載のトリフェニルアミン４量体が好まし
い。As a material constituting the hole transport layer, a derivative having triphenylamine as a basic skeleton is preferable. Examples thereof include a tetraphenylbenzidine compound, triphenylamine trimer and benzidine dimer described in JP-A-7-126615. Further, Japanese Unexamined Patent Publication No.
Various triphenyldiamine derivatives described in JP-A-48656 or MT described in JP-A-7-65958.
PD (commonly called TPD) may be used. In particular, Japanese Patent Application No. 9-34
Preferred is a triphenylamine tetramer described in No. 1238.
【００７０】電子輸送層を構成する材料としては、トリ
ス（８−キノリノラト）アルミニウム（以下Ａｌｑ）が
好ましい。他の例としてトリス（４−メチル−８−キノ
リノラト）アルミニウム等の金属錯体、３−（２´−ベ
ンゾチアゾリル）−７−ジエチルアミノクマリン等が挙
げられる。電子輸送層の膜厚は、１０〜１０００ｎｍと
することが好ましい。As a material constituting the electron transport layer, tris (8-quinolinolato) aluminum (hereinafter, Alq) is preferable. Other examples include metal complexes such as tris (4-methyl-8-quinolinolato) aluminum, 3- (2'-benzothiazolyl) -7-diethylaminocoumarin, and the like. The electron transport layer preferably has a thickness of 10 to 1000 nm.
【００７１】有機発光層を構成する材料としては、上記
Ａｌｑやその誘導体の他、これらにクマリン６やＤＣ
Ｍ、フェノキサゾン９といった色素をドープしてもよ
い。また、トリフェニルアミンにルブレンをドープした
り、ホール輸送層と電子輸送層の界面にバソクプロイン
等のホールブロック層を積層してホール輸送材料を発光
させてもよい。As materials constituting the organic light emitting layer, in addition to the above Alq and its derivatives, coumarin 6 and DC
M and a dye such as phenoxazone 9 may be doped. The hole transport material may emit light by doping rubrene into triphenylamine or laminating a hole block layer such as bathocuproine at the interface between the hole transport layer and the electron transport layer.
【００７２】上述のホール輸送層、電子輸送層、有機発
光層の各有機層については、アモルファス状態の均質な
膜を形成することが望ましく、真空蒸着法による成膜が
好ましい。さらに、真空中で連続して各層を形成するこ
とにより、各層間の界面に不純物が付着するのを防ぐこ
とによって、動作電圧の低下、高効率化、長寿命化とい
った特性の改善を図ることができる。また、これら各層
を真空蒸着法により形成するにあたり、一層に複数の化
合物を含有させる場合、化合物を入れた各ボートを個別
に温度制御して共蒸着することが好ましいが、あらかじ
め混合したものを蒸着しても良い。さらにこの他の成膜
方法として、溶液塗布法、ラングミュア・ブロジェット
（ＬＢ）法などを用いることもできる。溶液塗布法では
ポリマー等のマトリクス物質中に各化合物を分散させる
構成としても良い。Regarding the organic layers of the hole transport layer, the electron transport layer, and the organic light emitting layer, it is desirable to form a homogeneous film in an amorphous state, and it is preferable to form the film by a vacuum deposition method. Furthermore, by forming each layer continuously in a vacuum, by preventing impurities from adhering to the interface between each layer, it is possible to improve characteristics such as lower operating voltage, higher efficiency, and longer life. it can. In forming each of these layers by a vacuum deposition method, when a plurality of compounds are contained in one layer, it is preferable to co-deposit each boat containing the compounds by individually controlling the temperature. You may. Further, as other film forming methods, a solution coating method, a Langmuir-Blodgett (LB) method, or the like can be used. In the solution coating method, each compound may be dispersed in a matrix material such as a polymer.
【００７３】本願請求項１〜１４に記載の発明におい
て、その要部は有機電子注入層にある。有機電子注入層
に含まれる有機金属錯化合物とは、低仕事関数の金属で
あるアルカリ金属またはアルカリ土類金属を中心金属に
持ち、有機分子が配位した錯体を表す。In the invention as set forth in claims 1 to 14 of the present application, the main part is in the organic electron injection layer. The organometallic complex compound contained in the organic electron injecting layer refers to a complex having a low work function metal, an alkali metal or an alkaline earth metal, as a central metal and coordinated with organic molecules.
【００７４】一般に、ポルフィリン系化合物はホール注
入材料として有益であり、例えば特開昭６３−２６４６
９２号公報において、ホール注入帯を形成する材料とし
てフタロシアニン誘導体、ポルフィン誘導体が数多く列
挙されている。In general, porphyrin compounds are useful as hole injecting materials, for example, as described in JP-A-63-2646.
In Japanese Patent Publication No. 92, a number of phthalocyanine derivatives and porphine derivatives are listed as materials for forming a hole injection zone.
【００７５】一方、我々が検討した結果、本発明の（化
７）On the other hand, as a result of our investigation, it was found that
【００７６】[0076]
【化７】 Embedded image
【００７７】あるいは（化８）Or (Chemical Formula 8)
【００７８】[0078]
【化８】 Embedded image
【００７９】に表される化合物は、電子注入帯としての
効果を発現することが見出された。（化７）あるいは
（化８）の中心金属は、アルカリ金属またはアルカリ土
類金属であり、特には、低仕事関数の金属であるリチウ
ム、ナトリウム、カリウム、セシウム、マグネシウム、
カルシウムのいずれかが好ましい。この時、リチウム、
ナトリウム、カリウム、セシウム等１価のイオンの場合
は２個のイオンが必要で、マグネシウム、カルシウム等
２価のイオンの場合は１個のイオンが必要である。具体
的には Ｃ−１ ジリチウムフタロシアニン Ｃ−２ ジソディウムフタロシアニン Ｃ−３ ジポタシウムフタロシアニン Ｃ−４ マグネシウムフタロシアニン Ｃ−５ ジリチウムポルフィリン Ｃ−６ ジソディウムポルフィリン Ｃ−７ ジポタシウムポルフィリン Ｃ−８ ジセシウムポルフィリン Ｃ−９ ５，１０，１５，２０−テトラフェニルー２
１Ｈ、２３Ｈ−ポルフィン マグネシウム Ｃ−１０ ５，１０，１５，２０−テトラ（４−ピリジ
ル）―２１Ｈ、２３Ｈーポルフィン カルシウム 等が挙げられる。電子注入層を構成する材料に要求され
る特性としては、前述の通り、電子の注入特性だけでな
く、化学的あるいは物理的な安定性が求められる。フタ
ロシアニン化合物あるいはポルフィリン化合物の中心金
属は、分子中のピロール環と結合しているため化学的に
は安定であり、本発明の（化７）あるいは（化８）のよ
うに低仕事関数金属を有する化合物であっても安定であ
る。例えばジリチウムフタロシアニンをスライドガラス
に蒸着し大気中に放置しても、結晶化や変色など膜質の
変化は全く起こらず、単独膜としての安定性が示され
た。一方で、上述の中心金属は電子の授受に十分な特性
を保持しており、電子注入層を構成する材料として最適
である事が明らかになった。It has been found that the compound represented by the formula (1) exhibits an effect as an electron injection band. The central metal of (Chem. 7) or (Chem. 8) is an alkali metal or an alkaline earth metal, and particularly, a low work function metal such as lithium, sodium, potassium, cesium, magnesium,
Any of calcium is preferred. At this time, lithium,
In the case of monovalent ions such as sodium, potassium and cesium, two ions are required, and in the case of divalent ions such as magnesium and calcium, one ion is required. Specifically, C-1 dilithium phthalocyanine C-2 disodium phthalocyanine C-3 dipotassium phthalocyanine C-4 magnesium phthalocyanine C-5 dilithium porphyrin C-6 disodium porphyrin C-7 dipotassium porphyrin C-8 cesium Porphyrin C-9 5,10,15,20-tetraphenyl-2
1H, 23H-porphine magnesium C-10 5,10,15,20-tetra (4-pyridyl) -21H, 23H-porphine calcium and the like. As described above, the characteristics required for the material constituting the electron injection layer are not only the electron injection characteristics but also the chemical or physical stability. The central metal of the phthalocyanine compound or porphyrin compound is chemically stable because it is bonded to the pyrrole ring in the molecule, and has a low work function metal as in (Chem. 7) or (Chem. 8) of the present invention. Even compounds are stable. For example, even when dilithium phthalocyanine was vapor-deposited on a slide glass and left in the air, no change in film quality such as crystallization or discoloration occurred, indicating the stability as a single film. On the other hand, it became clear that the above-described central metal has sufficient properties for electron transfer, and is optimal as a material for forming the electron injection layer.
【００８０】次に電子不足化合物について説明する。現
在、中性分子間の結合の説明にはルイスーラングミュア
の原子価理論が用いられている。しかしながら十分な価
電子を持たない原子は８隅説を満たすことができない。
このように、原子価軌道数に比べ価電子数が少なく、８
隅説に従わない化合物を電子不足化合物と呼ぶ。電子不
足化合物を形成しやすい原子としてＬｉ，Ｂｅ，Ｍｇ，
Ｂ，Ｚｎ，Ａｌが挙げられる。例えば、無機化合物では
ＬｉＨ、ＢｅＨ２が該当する。またアルキル化Ａｌ等は
（化９）Next, the electron deficient compound will be described. At present, the valence theory of Lewis-Langmuir is used to explain the bond between neutral molecules. However, atoms without sufficient valence electrons cannot satisfy the eight corner theory.
Thus, the number of valence electrons is smaller than the number of valence orbitals, and 8
Compounds that do not follow the corner theory are called electron-deficient compounds. Li, Be, Mg,
B, Zn, and Al. For example, inorganic compounds include LiH and BeH2. In addition, alkylated Al etc.
【００８１】[0081]
【化９】 Embedded image
【００８２】のように３中心２電子結合を形成すること
により安定化している。電子不足化合物は閉殻を完成し
ていないため強い電子受容性を持っており、電子注入材
料として適していることを見出した。特に上述の通り、
有機化合物からなる電子注入層を用いることにより、有
機層との接合性の向上により、電子注入特性及び安定性
が向上する。具体的にはピラザボール構造を有する化合
物が好ましく、さらには Ｐ−１ ４，４，８，８−テトラキス（１Ｈ―ピラゾー
ルー１−イル）ピラザボール Ｐ−２ ４，４，８，８−テトラエチルピラザボール Ｐ−３ １，３，５，７−テトラメチルピラザボール Ｐ−４ ピラザボール が好ましい。これらの化合物は、電子輸送性も優れてお
り、厚膜化が可能である。従って、これらの化合物を電
子輸送層として用いた場合、電子注入層兼電子輸送層と
して一体化できる。As described above, stabilization is achieved by forming a three-center two-electron bond. It has been found that an electron-deficient compound has a strong electron-accepting property because it does not have a closed shell, and is suitable as an electron-injecting material. Especially as mentioned above,
By using the electron injection layer made of an organic compound, the bonding property with the organic layer is improved, so that the electron injection characteristics and stability are improved. Specifically, a compound having a pyrazaball structure is preferable. Further, P-1,4,4,8,8-tetrakis (1H-pyrazol-1-yl) pyrazaball P-2 4,4,8,8-tetraethylpyrazaball P-3 1,3,5,7-tetramethylpyrazaball P-4 pyrazaball is preferred. These compounds also have excellent electron transport properties, and can be made thick. Therefore, when these compounds are used as an electron transport layer, they can be integrated as an electron injection layer and an electron transport layer.
【００８３】本発明の有機電子注入層は有機化合物であ
るので、電子の注入に重要な接合面が有機／有機接合で
構成されることにより、従来の無機化合物からなる電子
注入層あるいは電子注入電極より構成される無機／有機
接合面に比べて相溶性が改善され、電子注入特性及び安
定性が向上する。これらの結果、発光効率が向上し、特
に寿命特性に対して飛躍的な効果が現れることが明らか
になった。Since the organic electron injecting layer of the present invention is an organic compound, a conventional electron injecting layer or electron injecting electrode made of an inorganic compound is formed by forming an organic / organic junction at a junction surface important for electron injection. Compatibility is improved as compared with the inorganic / organic joint surface constituted by the above, and electron injection characteristics and stability are improved. As a result, it has been clarified that the luminous efficiency is improved, and a dramatic effect is particularly exhibited on the life characteristics.
【００８４】これらの膜厚は０．１〜５ｎｍが好まし
く、特には０．２〜２ｎｍが好ましい。The thickness of these films is preferably from 0.1 to 5 nm, particularly preferably from 0.2 to 2 nm.
【００８５】有機電子注入層は、陰極と有機層との界面
に積層する。有機層の構成の一例として、図３の単層構
成、図４のＳＨ−Ａ型と呼ばれるホール輸送層／有機発
光層の積層構成、図５のＳＨ−Ｂ型と呼ばれる有機発光
層／電子輸送層の積層構成、図６のＤＨ型と呼ばれるホ
ール輸送層／有機発光層／電子輸送層の積層構成が挙げ
られる。各層を構成する材料は、上述の通りいずれも汎
用のものを広く用いることができる。また、それぞれの
層はイオン化ポテンシャル等を考慮して複数の層から構
成されてもよい。The organic electron injection layer is laminated on the interface between the cathode and the organic layer. As an example of the configuration of the organic layer, a single-layer configuration in FIG. 3, a layered configuration of a hole transport layer / organic light emitting layer called SH-A type in FIG. 4, and an organic light emitting layer / electron transport type called SH-B type in FIG. A layered structure of a layer, and a layered structure of a hole transport layer / organic light emitting layer / electron transport layer called a DH type in FIG. As described above, general-purpose materials can be widely used for each layer. Each layer may be composed of a plurality of layers in consideration of the ionization potential and the like.
【００８６】本願請求項１５〜２３に記載の発明におい
て、その要部は電子注入化合物を有機層に含むことにあ
る。電子注入化合物としては、アルカリ金属またはアル
カリ土類金属を中心金属に持つ有機金属錯化合物、フタ
ロシアニン化合物、ポルフィリン化合物あるいは電子不
足化合物等が好ましく、その電子注入特性及び安定性に
ついては上述の通りである。一般に有機物はホール輸送
能に優れた材料は多く存在するが、電子輸送性に優れた
材料は少なくまた移動度も小さい。これら電子注入化合
物を有機層中に含むことにより、電子を有機層中により
多く注入しキャリアバランスを改善することによって、
高輝度化、長寿命化を実現することができる。In the invention according to claims 15 to 23 of the present application, the essential part is that the organic layer contains an electron injection compound. As the electron injecting compound, an organometallic complex compound having an alkali metal or an alkaline earth metal as a central metal, a phthalocyanine compound, a porphyrin compound or an electron-deficient compound is preferred, and the electron injecting properties and stability are as described above. . In general, many organic materials have excellent hole transporting properties, but few materials have excellent electron transporting properties and low mobility. By including these electron injection compounds in the organic layer, by injecting more electrons into the organic layer and improving the carrier balance,
Higher brightness and longer life can be realized.
【００８７】電子注入化合物を含む有機層の構成とし
て、図７の単層構成においては有機発光層中に含む。積
層構成の場合は陰極側の有機層に含むのが好ましく、図
８のＳＨ−Ａ型では有機発光層中に、図９のＳＨ−Ｂ型
では電子輸送層中に、図１０のＤＨ型では電子輸送層中
に含むのが好ましく、さらにＤＨ型では電子輸送層と有
機発光層の両方に含んでもよい。電子注入化合物は０．
１〜９９．９％の濃度範囲において、層全体に均一に分
布してもよく、また陰極に近接するほど高濃度になるよ
うに階段状またはなだらかに濃度勾配をつけてもよい。The organic layer containing the electron injecting compound is included in the organic light emitting layer in the single layer configuration shown in FIG. In the case of a laminated structure, it is preferable to include it in the organic layer on the cathode side, in the organic light emitting layer in the SH-A type in FIG. 8, in the electron transport layer in the SH-B type in FIG. 9, and in the DH type in FIG. It is preferably contained in the electron transport layer, and in the case of the DH type, it may be contained in both the electron transport layer and the organic light emitting layer. The electron injecting compound is 0.
In the concentration range of 1 to 99.9%, the concentration may be uniformly distributed over the entire layer, or the concentration may be stepwise or gently increased so that the concentration becomes higher as the position becomes closer to the cathode.
【００８８】本願請求項２４〜３２に記載の発明におい
て、その要部は電子注入化合物を有機層の陰極側に含む
ことにあり、陰極に発生した電子を効率的に有機層中へ
注入することができる。電子注入化合物としては、アル
カリ金属またはアルカリ土類金属を中心金属に持つ有機
金属錯化合物、フタロシアニン化合物、ポルフィリン化
合物あるいは電子不足化合物等が好ましく、その電子注
入特性及び安定性については上述の通りである。In the invention according to claims 24 to 32 of the present application, the essential part is that the electron injection compound is included on the cathode side of the organic layer, and the electrons generated at the cathode are efficiently injected into the organic layer. Can be. As the electron injecting compound, an organometallic complex compound having an alkali metal or an alkaline earth metal as a central metal, a phthalocyanine compound, a porphyrin compound or an electron-deficient compound is preferred, and the electron injecting properties and stability are as described above. .
【００８９】電子注入化合物を含む有機層の構成とし
て、図７の単層構成においては有機発光層の陰極側に含
む。積層構成の場合は陰極側の有機層に含むのが好まし
く、図８のＳＨ−Ａ型では有機発光層の陰極側に、図９
のＳＨ−Ｂ型では電子輸送層の陰極側に、図１０のＤＨ
型では電子輸送層の陰極側に含むのが好ましい。電子注
入化合物は、上記層の陰極側２／３程度までの範囲内に
０．１〜９９．９％の濃度範囲において、均一に分布し
てもよく、また陰極に近接するほど高濃度になるように
階段状またはなだらかに濃度勾配をつけてもよい。The organic layer containing the electron injecting compound is included on the cathode side of the organic light emitting layer in the single layer configuration shown in FIG. In the case of the laminated structure, it is preferable that the organic layer is included in the organic layer on the cathode side. In the case of the SH-A type shown in FIG.
In the SH-B type, the DH shown in FIG.
In the case of the mold, it is preferably contained on the cathode side of the electron transport layer. The electron injecting compound may be uniformly distributed in a concentration range of 0.1 to 99.9% within a range up to about 2/3 of the layer on the cathode side, and the concentration becomes higher as the layer is closer to the cathode. As described above, the concentration gradient may be applied stepwise or gently.
【００９０】陰極は、本発明の有機電子注入層を積層す
ることにより、あるいは有機層に電子注入化合物を含む
ことにより、低仕事関数の不安定な金属を用いる必要は
なく、仕事関数が４．０ｅＶ以上の安定な金属を用いる
ことができる。例えば、Ａｌ、Ａｇ、Ｉｎ、Ｂｉ等の金
属が挙げられ、これらの中の一種でもよく、複数組み合
わせて合金あるいは積層膜を形成してもよい。膜厚は厚
く積層してもよく、１０〜１０００ｎｍが好ましい。こ
れら陰極の形成には蒸着法やスパッタ法が好ましい。The cathode does not need to use an unstable metal having a low work function by laminating the organic electron injecting layer of the present invention or by including an electron injecting compound in the organic layer. A stable metal of 0 eV or more can be used. For example, metals such as Al, Ag, In, and Bi may be mentioned, and one of them may be used, or a plurality of them may be combined to form an alloy or a laminated film. The film may be laminated thickly, preferably 10 to 1000 nm. For forming these cathodes, a vapor deposition method or a sputtering method is preferable.
【００９１】本願請求項４１〜４４に記載の発明におい
て、その要部はアルカリ金属またはアルカリ土類金属を
中心金属に持つ有機金属錯化合物、フタロシアニン化合
物、ポルフィリン化合物あるいは電子不足化合物等を含
む有機電子注入層を積層する工程を有することにあり、
従来電子注入特性を担ってきたアルカリ金属、アルカリ
土類金属またはこれらの化合物を含む電子注入電極また
は電子注入層を積層する工程に変わるものであればよ
い。有機電子注入層は有機発光層などの有機層と同様、
真空蒸着法の他、溶液塗布法、ＬＢ法等を用いることが
できる。In the invention as set forth in claims 41 to 44 of the present application, the main part is an organic electron compound including an organic metal complex compound having an alkali metal or an alkaline earth metal as a central metal, a phthalocyanine compound, a porphyrin compound or an electron-deficient compound. Having a step of laminating the injection layer,
Any method may be used as long as it replaces the step of laminating an electron injection electrode or an electron injection layer containing an alkali metal, an alkaline earth metal, or a compound thereof, which has conventionally been responsible for electron injection characteristics. The organic electron injection layer is similar to an organic layer such as an organic light emitting layer,
In addition to the vacuum deposition method, a solution coating method, an LB method, or the like can be used.
【００９２】本願請求項４５〜４８に記載の発明におい
て、その要部はアルカリ金属またはアルカリ土類金属を
中心金属に持つ有機金属錯化合物、フタロシアニン化合
物、ポルフィリン化合物あるいは電子不足化合物等を有
機層または有機層の陰極側に含む工程を有することにあ
る。In the invention as set forth in claims 45 to 48 of the present application, the essential part is that an organic metal complex compound having an alkali metal or an alkaline earth metal as a central metal, a phthalocyanine compound, a porphyrin compound, an electron-deficient compound, etc. In other words, the method includes a step including the organic layer on the cathode side.
【００９３】これらの工程は、従来用いられてきたアル
カリ金属またはアルカリ土類金属を含む金属電極を形成
する工程に比べて、作業性、再現性に優れ、工程中での
特性劣化がなく制御が容易であるため、製造工程の信頼
性向上と歩留まりを改善できるものである。These steps are more excellent in workability and reproducibility than in the step of forming a metal electrode containing an alkali metal or an alkaline earth metal which has been conventionally used, and the control is performed without deterioration of characteristics in the steps. Since it is easy, the reliability of the manufacturing process and the yield can be improved.
【００９４】次に具体的な実施例に基づいてさらに詳細
に説明する。Next, the present invention will be described in more detail based on specific embodiments.
【００９５】（実施例１）ポリビニルカルバゾールと２
−（４−ビフェニリル）―５−（４−ｔ−ブチルフェニ
ル）―１，３，４−オキサジアゾールとレーザー色素ク
マリン６を１００：４０：０．２の割合でトルエン：Ｔ
ＨＦ＝１：１混合溶媒中に溶解した溶液を、ＩＴＯを成
膜したガラス基板上にスピナーで塗布し、膜厚１００ｎ
ｍの有機発光層を形成した。この上にジリチウムフタロ
シアニン（Ｃ−１）を０．５，１，２ｎｍと３種類の膜
厚からなる有機電子注入層を形成し、最後にＡｌからな
る陰極を１００ｎｍ形成した。各膜厚の有機電子注入層
を形成した有機発光素子に直流電圧を印可して評価した
ところ、いずれも１０Ｖで約５００ｃｄ／ｍ2であり、
発光効率は２．８ｃｄ／Ａと、ばらつきのない安定な発
光が得られた。これらの素子を初期輝度３００ｃｄ／ｍ
2で定電流連続点灯試験を行ったところ、輝度半減期は
約３００時間であった。Example 1 Polyvinylcarbazole and 2
-(4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole and laser dye coumarin 6 in a ratio of 100: 40: 0.2 in toluene: T
A solution dissolved in a mixed solvent of HF = 1: 1 was applied on a glass substrate on which ITO was formed by a spinner, and the film thickness was 100 n.
m organic light emitting layers were formed. An organic electron injecting layer having three types of film thicknesses of dilithium phthalocyanine (C-1) of 0.5, 1, and 2 nm was formed thereon, and finally a cathode made of Al was formed to a thickness of 100 nm. When a direct current voltage was applied to the organic light emitting device having the organic electron injection layer of each film thickness and evaluated, all were about 500 cd / m 2 at 10 V,
The luminous efficiency was 2.8 cd / A, and stable luminescence without variation was obtained. These elements were set to have an initial luminance of 300 cd / m.
When a constant current continuous lighting test was performed in 2 , the luminance half life was about 300 hours.
【００９６】（実施例２）ＩＴＯを成膜したガラス基板
上に、Ｎ，Ｎ′−ジフェニルーＮ，Ｎ′−ビス（３−メ
チルフェニル）―１，１′−ビフェニル―４，４′−ジ
アミンからなる５０ｎｍの膜厚のホール輸送層を形成
し、続いて有機発光層として、トリス（８−キノリノラ
ト）アルミニウムを５０ｎｍ蒸着した。引き続き、ジリ
チウムフタロシアニン（Ｃ−１）を０．５，１，２ｎｍ
と３種類の膜厚からなる有機電子注入層を形成し、最後
にＡｌからなる陰極を１００ｎｍ形成した。各膜厚の有
機電子注入層を形成した有機発光素子に直流電圧を印可
して評価したところ、いずれも５Ｖで約５００ｃｄ／ｍ
2であり、発光効率は４．３ｃｄ／Ａと、ばらつきのな
い安定な発光が得られた。これらの素子を初期輝度３０
０ｃｄ／ｍ2で定電流連続点灯試験を行ったところ、輝
度半減期は約５００時間であった。(Example 2) N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine was formed on a glass substrate on which ITO was formed. Then, a hole transport layer having a thickness of 50 nm was formed, followed by vapor deposition of 50 nm of tris (8-quinolinolato) aluminum as an organic light emitting layer. Subsequently, dilithium phthalocyanine (C-1) was added to 0.5, 1, 2 nm.
And an organic electron injection layer having three film thicknesses, and finally a cathode made of Al having a thickness of 100 nm. When a DC voltage was applied to the organic light emitting device having the organic electron injection layer of each film thickness and evaluated, all were about 500 cd / m at 5 V.
2 , and the light emission efficiency was 4.3 cd / A, and stable light emission with no variation was obtained. These elements are provided with an initial luminance of 30
When a constant current continuous lighting test was performed at 0 cd / m 2 , the luminance half life was about 500 hours.
【００９７】（実施例３）ＩＴＯを成膜したガラス基板
上に、Ｎ，Ｎ′−ビス（４‘―ジフェニルアミノー４−
ビフェニリル）ーＮ，Ｎ′−ジフェニルベンジジンと２
ｗｔ％のルブレンからなる５０ｎｍの膜厚の有機発光層
を形成し、続いて電子輸送層として、トリス（４−メチ
ルー８−キノリノラト）アルミニウムを５０ｎｍ蒸着し
た。引き続き、ジリチウムフタロシアニン（Ｃ−１）を
０．５，１，２ｎｍと３種類の膜厚からなる有機電子注
入層を形成し、最後にＡｌからなる陰極を１００ｎｍ形
成した。各膜厚の有機電子注入層を形成した有機発光素
子に直流電圧を印可して評価したところ、いずれも４Ｖ
で約５００ｃｄ／ｍ2であり、発光効率は８．５ｃｄ／
Ａと、ばらつきのない安定な発光が得られた。これらの
素子を初期輝度３００ｃｄ／ｍ2で定電流連続点灯試験
を行ったところ、輝度半減期は約１００００時間であっ
た。Example 3 N, N'-bis (4'-diphenylamino-4-) was formed on a glass substrate on which ITO was formed.
Biphenylyl) -N, N'-diphenylbenzidine and 2
An organic light-emitting layer having a thickness of 50 nm made of rubrene of wt% was formed, and then, as an electron transport layer, tris (4-methyl-8-quinolinolato) aluminum was deposited to a thickness of 50 nm. Subsequently, an organic electron injecting layer having three types of film thicknesses of dilithium phthalocyanine (C-1) of 0.5, 1, and 2 nm was formed, and finally a cathode made of Al was formed to a thickness of 100 nm. When a direct current voltage was applied to the organic light emitting device having the organic electron injection layer of each thickness formed thereon, the evaluation was 4 V in each case.
Is about 500 cd / m 2 , and the luminous efficiency is 8.5 cd / m 2.
A and stable light emission without variation was obtained. When these elements were subjected to a constant current continuous lighting test at an initial luminance of 300 cd / m 2 , the luminance half life was about 10,000 hours.
【００９８】（実施例４）ＩＴＯを成膜したガラス基板
上に、Ｎ，Ｎ′−ジフェニルーＮ，Ｎ′−ビス（３−メ
チルフェニル）―１，１′−ビフェニル―４，４′−ジ
アミンからなる５０ｎｍの膜厚のホール輸送層を形成
し、続いて有機発光層として、トリス（８−キノリノラ
ト）アルミニウムと０．５ｗｔ％のキナクリドンを２０
ｎｍ蒸着し、続いて電子輸送層としてトリス（８−キノ
リノラト）アルミニウムを３０ｎｍ蒸着した。引き続
き、ジリチウムフタロシアニン（Ｃ−１）を０．５，
１，２ｎｍと３種類の膜厚からなる有機電子注入層を形
成し、最後にＡｌからなる陰極を１００ｎｍ形成した。
各膜厚の有機電子注入層を形成した有機発光素子に直流
電圧を印可して評価したところ、いずれも４．５Ｖで約
５００ｃｄ／ｍ2であり、発光効率は１０ｃｄ／Ａと、
ばらつきのない安定な発光が得られた。これらの素子を
初期輝度３００ｃｄ／ｍ2で定電流連続点灯試験を行っ
たところ、輝度半減期は約６００時間であった。(Example 4) N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine was formed on a glass substrate on which ITO was formed. A 50 nm-thick hole transport layer is formed, and then tris (8-quinolinolato) aluminum and 0.5 wt% quinacridone are used as an organic light emitting layer.
Next, 30 nm of tris (8-quinolinolato) aluminum was deposited as an electron transport layer. Subsequently, dilithium phthalocyanine (C-1) was added to 0.5,
An organic electron injection layer having three film thicknesses of 1, 2 nm was formed, and finally a cathode made of Al was formed to a thickness of 100 nm.
When a DC voltage was applied to the organic light emitting device having the organic electron injection layer of each film thickness and evaluated, all were about 500 cd / m 2 at 4.5 V, and the luminous efficiency was 10 cd / A.
Stable light emission without variation was obtained. When these elements were subjected to a constant current continuous lighting test at an initial luminance of 300 cd / m 2 , the luminance half life was about 600 hours.
【００９９】（実施例５）実施例２の有機電子注入層の
形成において、ジリチウムフタロシアニン（Ｃ−１）の
代わりに、ジソディウムフタロシアニン（Ｃ−２）、マ
グネシウムフタロシアニン（Ｃ−４）、ジポタシウムポ
ルフィリン（Ｃ−７）、５，１０，１５，２０−テトラ
フェニルーポルフィン マグネシウム（Ｃ−９）、５，
１０，１５，２０−テトラ（４−ピリジル）ーポルフィ
ン カルシウム（Ｃ−１０）、４，４，８，８−テトラ
キス（１Ｈ―ピラゾールー１−イル）ピラザボール（Ｐ
−１）、１，３，５，７−テトラメチルピラザボール
（Ｐ−３）を用いた以外は実施例２と同様にして有機発
光素子を作製した。比較例として有機電子注入層の代わ
りにＬｉからなる電子注入電極を形成した。これらの素
子に直流電圧を印可して評価し、発光効率を（表１）
に、初期輝度３００ｃｄ／ｍ2で定電流連続点灯試験し
た時の輝度半減期を（表２）に示す。(Example 5) In forming the organic electron injection layer of Example 2, instead of dilithium phthalocyanine (C-1), disodium phthalocyanine (C-2), magnesium phthalocyanine (C-4), Potassium porphyrin (C-7), 5,10,15,20-tetraphenyl-porphine magnesium (C-9), 5,
10,15,20-Tetra (4-pyridyl) -porphine calcium (C-10), 4,4,8,8-tetrakis (1H-pyrazol-1-yl) pyrazaball (P
-1) An organic light-emitting device was produced in the same manner as in Example 2, except that 1,3,5,7-tetramethylpyrazaball (P-3) was used. As a comparative example, an electron injection electrode made of Li was formed instead of the organic electron injection layer. The luminous efficiency was evaluated by applying a DC voltage to these devices (Table 1).
Table 2 shows the luminance half-life of a constant current continuous lighting test at an initial luminance of 300 cd / m 2 .
【０１００】[0100]
【表１】 [Table 1]
【０１０１】[0101]
【表２】 [Table 2]
【０１０２】比較例のＬｉからなる電子注入電極を形成
した有機発光素子は、Ｌｉ膜厚の増加と共に発光効率が
わずかづつ低下した。また、駆動電圧の上昇も見られ
た。これは、Ｌｉ薄膜が成膜中あるいは成膜後に酸化さ
れるなどして劣化したためと考えられる。一方、本発明
の有機電子注入層を形成した有機発光素子は膜厚依存性
がなく、高輝度で、長期安定性に優れていることがわか
る。In the organic light-emitting device having the electron injection electrode made of Li of the comparative example, the luminous efficiency slightly decreased as the Li film thickness increased. In addition, an increase in driving voltage was also observed. This is probably because the Li thin film was deteriorated by being oxidized during or after the film formation. On the other hand, it can be seen that the organic light-emitting device having the organic electron-injecting layer of the present invention does not depend on the film thickness, has high luminance, and has excellent long-term stability.
【０１０３】（実施例６）ポリビニルカルバゾールと２
−（４−ビフェニリル）―５−（４−ｔ−ブチルフェニ
ル）―１，３，４−オキサジアゾールとレーザー色素ク
マリン６と４，４，８，８−テトラキス（１Ｈ―ピラゾ
ールー１−イル）ピラザボール（Ｐ−１）を１００：４
０：０．２：１０の割合でトルエン：ＴＨＦ＝１：１混
合溶媒中に溶解した溶液を、ＩＴＯを成膜したガラス基
板上にスピナーで塗布し、膜厚１００ｎｍの有機発光層
を形成した。この上にＡｌからなる陰極を１００ｎｍ形
成した。このようにして得た有機発光素子に直流電圧を
印可して評価したところ、８Ｖで約５００ｃｄ／ｍ2で
あり、発光効率は３．２ｃｄ／Ａと、安定な発光が得ら
れた。また、初期輝度３００ｃｄ／ｍ2で定電流連続点
灯試験を行ったところ、輝度半減期は約３５０時間であ
った。(Example 6) Polyvinyl carbazole and 2
-(4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole and laser dye coumarin 6 and 4,4,8,8-tetrakis (1H-pyrazol-1-yl) Pilaza ball (P-1) 100: 4
A solution dissolved in a mixed solvent of toluene: THF = 1: 1 at a ratio of 0: 0.2: 10 was applied on a glass substrate on which an ITO film was formed by a spinner to form an organic light emitting layer having a thickness of 100 nm. . On this, a 100 nm cathode made of Al was formed. When a DC voltage was applied to the organic light-emitting device thus obtained and evaluated, it was about 500 cd / m 2 at 8 V, and the luminous efficiency was 3.2 cd / A, and stable light emission was obtained. When a constant current continuous lighting test was performed at an initial luminance of 300 cd / m 2 , the luminance half life was about 350 hours.
【０１０４】（実施例７）ＩＴＯを成膜したガラス基板
上に、Ｎ，Ｎ′−ジフェニルーＮ，Ｎ′−ビス（３−メ
チルフェニル）―１，１′−ビフェニル―４，４′−ジ
アミンからなる５０ｎｍの膜厚のホール輸送層を形成
し、続いて有機発光層として、トリス（８−キノリノラ
ト）アルミニウムを５０ｎｍ蒸着する際、１０ｗｔ％の
４，４，８，８−テトラキス（１Ｈ―ピラゾールー１−
イル）ピラザボール（Ｐ−１）を共蒸着した。最後にＡ
ｌからなる陰極を１００ｎｍ形成した。このようにして
得た有機発光素子に直流電圧を印可して評価したとこ
ろ、５Ｖで約５００ｃｄ／ｍ2であり、発光効率は４．
５ｃｄ／Ａと、安定な発光が得られた。また初期輝度３
００ｃｄ／ｍ2で定電流連続点灯試験を行ったところ、
輝度半減期は約５８０時間であった。(Example 7) N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine was formed on a glass substrate on which ITO was formed. When a hole transport layer having a thickness of 50 nm is formed, and then tris (8-quinolinolato) aluminum is deposited to a thickness of 50 nm as an organic light emitting layer, 10 wt% of 4,4,8,8-tetrakis (1H-pyrazole-aluminum) is deposited. 1-
Il) Pilaza ball (P-1) was co-evaporated. Finally A
1 was formed to a thickness of 100 nm. When a DC voltage was applied to the organic light-emitting device thus obtained and evaluated, it was about 500 cd / m 2 at 5 V, and the luminous efficiency was 4.
A stable light emission of 5 cd / A was obtained. In addition, initial brightness 3
When a constant current continuous lighting test was performed at 00 cd / m 2 ,
The luminance half life was about 580 hours.
【０１０５】（実施例８）ＩＴＯを成膜したガラス基板
上に、Ｎ，Ｎ′−ビス（４‘―ジフェニルアミノー４−
ビフェニリル）ーＮ，Ｎ′−ジフェニルベンジジンと２
ｗｔ％のルブレンからなる５０ｎｍの膜厚の有機発光層
を形成し、続いて電子輸送層として、トリス（４−メチ
ルー８−キノリノラト）アルミニウムを５０ｎｍ蒸着す
る際、１０ｗｔ％の４，４，８，８−テトラキス（１Ｈ
―ピラゾールー１−イル）ピラザボール（Ｐ−１）を共
蒸着した。最後にＡｌからなる陰極を１００ｎｍ形成し
た。このようにして得た有機発光素子に直流電圧を印可
して評価したところ、４Ｖで約５５０ｃｄ／ｍ2であ
り、発光効率は８．６ｃｄ／Ａと、安定な発光が得られ
た。また初期輝度３００ｃｄ／ｍ2で定電流連続点灯試
験を行ったところ、輝度半減期は約１２０００時間であ
った。Example 8 N, N'-bis (4'-diphenylamino-4-) was formed on a glass substrate on which ITO was formed.
Biphenylyl) -N, N'-diphenylbenzidine and 2
When an organic light emitting layer having a thickness of 50 nm made of rubrene of wt% is formed, and then, as an electron transporting layer, tris (4-methyl-8-quinolinolato) aluminum is deposited to a thickness of 50 nm. 8-tetrakis (1H
-Pyrazol-1-yl) pyraza ball (P-1) was co-evaporated. Finally, a 100 nm thick cathode made of Al was formed. When a DC voltage was applied to the organic light-emitting device thus obtained and evaluated, it was about 550 cd / m 2 at 4 V, and luminescence efficiency was 8.6 cd / A, and stable light emission was obtained. When a constant current continuous lighting test was performed at an initial luminance of 300 cd / m 2 , the luminance half life was about 12000 hours.
【０１０６】（実施例９）ＩＴＯを成膜したガラス基板
上に、Ｎ，Ｎ′−ジフェニルーＮ，Ｎ′−ビス（３−メ
チルフェニル）―１，１′−ビフェニル―４，４′−ジ
アミンからなる５０ｎｍの膜厚のホール輸送層を形成
し、続いて有機発光層としてトリス（８−キノリノラ
ト）アルミニウムと０．５ｗｔ％のキナクリドンを２０
ｎｍ蒸着し、続いて電子輸送層としてトリス（８−キノ
リノラト）アルミニウムを３０ｎｍ蒸着する際、１０ｗ
ｔ％の４，４，８，８−テトラキス（１Ｈ―ピラゾール
ー１−イル）ピラザボール（Ｐ−１）を共蒸着した。最
後にＡｌからなる陰極を１００ｎｍ形成した。このよう
にして得た有機発光素子に直流電圧を印可して評価した
ところ、４．５Ｖで約５２０ｃｄ／ｍ2であり、発光効
率は９．８ｃｄ／Ａと安定な発光が得られた。また初期
輝度３００ｃｄ／ｍ2で定電流連続点灯試験を行ったと
ころ、輝度半減期は約７００時間であった。Example 9 N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine was formed on a glass substrate on which ITO was formed. A hole transport layer having a thickness of 50 nm is formed of tris (8-quinolinolato) aluminum and 0.5 wt% of quinacridone as an organic light emitting layer.
When depositing 30 nm of tris (8-quinolinolato) aluminum as an electron transporting layer, 10 w
4,4,8,8-Tetrakis (1H-pyrazol-1-yl) pyraza ball (P-1) of t% was co-deposited. Finally, a 100 nm thick cathode made of Al was formed. When a DC voltage was applied to the organic light-emitting device thus obtained and evaluated, it was about 520 cd / m 2 at 4.5 V, and luminescence efficiency was 9.8 cd / A, and stable light emission was obtained. When a constant current continuous lighting test was performed at an initial luminance of 300 cd / m 2 , the luminance half life was about 700 hours.
【０１０７】（実施例１０）実施例７の有機発光層の形
成において、４，４，８，８−テトラキス（１Ｈ―ピラ
ゾールー１−イル）ピラザボール（Ｐ−１）の代わり
に、ジリチウムフタロシアニン（Ｃ−１）、ジソディウ
ムフタロシアニン（Ｃ−２）、マグネシウムフタロシア
ニン（Ｃ−４）、ジポタシウムポルフィリン（Ｃ−
７）、５，１０，１５，２０−テトラフェニルーポルフ
ィン マグネシウム（Ｃ−９）、５，１０，１５，２０
−テトラ（４−ピリジル）ーポルフィン カルシウム
（Ｃ−１０）、１，３，５，７−テトラメチルピラザボ
ール（Ｐ−３）を用いた以外は実施例７と同様にして有
機発光素子を作製した。これらの素子に直流電圧を印可
して評価し、発光効率を（表１）に、初期輝度３００ｃ
ｄ／ｍ2で定電流連続点灯試験した時の輝度半減期を
（表２）に示す。Example 10 In the formation of the organic light emitting layer of Example 7, dilithium phthalocyanine (P-1) was used instead of 4,4,8,8-tetrakis (1H-pyrazol-1-yl) pyrazabole (P-1). C-1), disodium phthalocyanine (C-2), magnesium phthalocyanine (C-4), dipotassium porphyrin (C-
7), 5,10,15,20-tetraphenyl-porphine magnesium (C-9), 5,10,15,20
-Tetra (4-pyridyl) -porphine Preparation of an organic light-emitting device in the same manner as in Example 7 except that calcium (C-10) and 1,3,5,7-tetramethylpyrazaball (P-3) were used. did. These elements were evaluated by applying a DC voltage, and the luminous efficiency was set to (Table 1), and the initial luminance was set to 300c.
(Table 2) shows the half life of the luminance when the constant current continuous lighting test was performed at d / m 2 .
【０１０８】（実施例１１）ＩＴＯを成膜したガラス基
板上に、Ｎ，Ｎ′−ジフェニルーＮ，Ｎ′−ビス（３−
メチルフェニル）―１，１′−ビフェニル―４，４′−
ジアミンからなる有機発光層を１００ｎｍ蒸着する際、
まず７０ｎｍ蒸着し終わったところでピラザボール（Ｐ
−４）を１０ｗｔ％含むように飛ばし始め、３０ｎｍの
膜厚にわたって共蒸着を行った。この上にＡｌからなる
陰極を１００ｎｍ形成した。このようにして得た有機発
光素子に直流電圧を印可して評価したところ、１０Ｖで
約４５０ｃｄ／ｍ2であり、発光効率は１．５ｃｄ／Ａ
と、安定な発光が得られた。また初期輝度３００ｃｄ／
ｍ2で定電流連続点灯試験を行ったところ、輝度半減期
は約２００時間であった。(Example 11) N, N'-diphenyl-N, N'-bis (3-
Methylphenyl) -1,1'-biphenyl-4,4'-
When depositing an organic light emitting layer made of diamine to 100 nm,
First, at the end of 70 nm deposition, Pilaza ball (P
-4) was started so as to contain 10 wt%, and co-evaporation was performed over a film thickness of 30 nm. On this, a 100 nm cathode made of Al was formed. When a DC voltage was applied to the organic light-emitting device obtained in this way and evaluated, it was about 450 cd / m 2 at 10 V, and the luminous efficiency was 1.5 cd / A.
, Stable light emission was obtained. The initial luminance is 300 cd /
When a constant current continuous lighting test was conducted at m 2 , the luminance half life was about 200 hours.
【０１０９】（実施例１２）ＩＴＯを成膜したガラス基
板上に、Ｎ，Ｎ′−ジフェニルーＮ，Ｎ′−ビス（３−
メチルフェニル）―１，１′−ビフェニル―４，４′−
ジアミンからなる５０ｎｍの膜厚のホール輸送層を形成
し、続いて有機発光層として、トリス（８−キノリノラ
ト）アルミニウムを５０ｎｍ蒸着する際、まず２５ｎｍ
蒸着し終わったところでピラザボール（Ｐ−４）を１０
ｗｔ％含むように飛ばし始め、２５ｎｍの膜厚にわたっ
て共蒸着を行った。最後にＡｌからなる陰極を１００ｎ
ｍ形成した。このようにして得た有機発光素子に直流電
圧を印可して評価したところ、５Ｖで約４５０ｃｄ／ｍ
2であり、発光効率は４．３ｃｄ／Ａと、安定な発光が
得られた。また初期輝度３００ｃｄ／ｍ2で定電流連続
点灯試験を行ったところ、輝度半減期は約５００時間で
あった。(Example 12) N, N'-diphenyl-N, N'-bis (3-
Methylphenyl) -1,1'-biphenyl-4,4'-
A 50-nm thick hole transport layer made of diamine is formed, and subsequently, as an organic light emitting layer, tris (8-quinolinolato) aluminum is deposited to a thickness of 50 nm.
At the end of vapor deposition, add 10 Pilaza balls (P-4).
Co-evaporation was performed over a film thickness of 25 nm. Finally, the cathode made of Al is 100n
m was formed. The obtained organic light-emitting device was evaluated by applying a DC voltage to it.
2 , and the luminous efficiency was 4.3 cd / A, and stable luminescence was obtained. When a constant current continuous lighting test was performed at an initial luminance of 300 cd / m 2 , the luminance half life was about 500 hours.
【０１１０】（実施例１３）ＩＴＯを成膜したガラス基
板上に、Ｎ，Ｎ′−ビス（４‘―ジフェニルアミノー４
−ビフェニリル）ーＮ，Ｎ′−ジフェニルベンジジンと
２ｗｔ％のルブレンからなる５０ｎｍの膜厚の有機発光
層を形成し、続いて電子輸送層として、トリス（４−メ
チルー８−キノリノラト）アルミニウムを５０ｎｍ蒸着
する際、まず４０ｎｍ蒸着し終わったところでピラザボ
ール（Ｐ−４）を１０ｗｔ％含むように飛ばし始め、１
０ｎｍの膜厚にわたって共蒸着を行った。最後にＡｌか
らなる陰極を１００ｎｍ形成した。このようにして得た
有機発光素子に直流電圧を印可して評価したところ、
４．５Ｖで約５５０ｃｄ／ｍ2であり、発光効率は８．
６ｃｄ／Ａと、安定な発光が得られた。また初期輝度３
００ｃｄ／ｍ2で定電流連続点灯試験を行ったところ、
輝度半減期は約１０５００時間であった。(Example 13) N, N'-bis (4'-diphenylamino-4) was formed on a glass substrate on which ITO was formed.
-Biphenylyl) -N, N'-diphenylbenzidine and 2 wt% of rubrene to form an organic light emitting layer having a thickness of 50 nm, and subsequently, as an electron transport layer, tris (4-methyl-8-quinolinolato) aluminum to a thickness of 50 nm. First, when the deposition of 40 nm was completed, the flying of the pyrazer ball (P-4) was started so as to contain 10 wt%.
Co-evaporation was performed over a film thickness of 0 nm. Finally, a 100 nm thick cathode made of Al was formed. When a DC voltage was applied to the organic light emitting device thus obtained and evaluated,
It is about 550 cd / m 2 at 4.5 V, and the luminous efficiency is 8.
A stable light emission of 6 cd / A was obtained. In addition, initial brightness 3
When a constant current continuous lighting test was performed at 00 cd / m 2 ,
The luminance half life was about 10500 hours.
【０１１１】（実施例１４）ＩＴＯを成膜したガラス基
板上に、Ｎ，Ｎ′−ジフェニルーＮ，Ｎ′−ビス（３−
メチルフェニル）―１，１′−ビフェニル―４，４′−
ジアミンからなる５０ｎｍの膜厚のホール輸送層を形成
し、続いて有機発光層として、トリス（８−キノリノラ
ト）アルミニウムと０．５ｗｔ％のキナクリドンを２０
ｎｍ蒸着し、続いて電子輸送層としてトリス（８−キノ
リノラト）アルミニウムを３０ｎｍ蒸着する際、まず２
０ｎｍ蒸着し終わったところでピラザボール（Ｐ−４）
を１０ｗｔ％含むように飛ばし始め、１０ｎｍの膜厚に
わたって共蒸着を行った。最後にＡｌからなる陰極を１
００ｎｍ形成した。このようにして得た有機発光素子に
直流電圧を印可して評価したところ、５．０Ｖで約５０
０ｃｄ／ｍ2であり、発光効率は１０ｃｄ／Ａと、安定
な発光が得られた。また初期輝度３００ｃｄ／ｍ 2で定
電流連続点灯試験を行ったところ、輝度半減期は約７０
０時間であった。(Example 14) Glass substrate on which ITO was formed
On a plate, N, N'-diphenyl-N, N'-bis (3-
Methylphenyl) -1,1'-biphenyl-4,4'-
Forming a 50 nm thick hole transport layer made of diamine
Subsequently, tris (8-quinolinola) was used as an organic light emitting layer.
G) 20 parts of aluminum and 0.5 wt% of quinacridone
nm followed by tris (8-quino
Linolato) When depositing 30 nm of aluminum,
Pila ball (P-4) after 0nm deposition
Start to fly to contain 10wt%
Co-evaporation was performed over. Finally, replace the cathode made of Al with 1
00 nm was formed. The organic light emitting device obtained in this way
When a DC voltage was applied and evaluated, it was about 50 at 5.0 V.
0 cd / mTwoAnd the luminous efficiency is stable at 10 cd / A.
Light emission was obtained. The initial luminance is 300 cd / m TwoFixed in
When the current continuous lighting test was performed, the luminance half life was about 70.
It was 0 hours.
【０１１２】（実施例１５）実施例１２の有機発光層の
形成において、ピラザボール（Ｐ−４）の代わりに、ジ
リチウムフタロシアニン（Ｃ−１）、ジソディウムフタ
ロシアニン（Ｃ−２）、マグネシウムフタロシアニン
（Ｃ−４）、ジポタシウムポルフィリン（Ｃ−７）、
５，１０，１５，２０−テトラフェニルーポルフィン
マグネシウム（Ｃ−９）、５，１０，１５，２０−テト
ラ（４−ピリジル）ーポルフィン カルシウム（Ｃ−１
０）、４，４，８，８−テトラキス（１Ｈ―ピラゾール
ー１−イル）ピラザボール（Ｐ−１）１，３，５，７−
テトラメチルピラザボール（Ｐ−３）を用いた以外は実
施例１２と同様にして有機発光素子を作製した。これら
の素子に直流電圧を印可して評価し、発光効率を（表
１）に、初期輝度３００ｃｄ／ｍ2で定電流連続点灯試
験した時の輝度半減期を（表２）に示す。Example 15 In the formation of the organic light emitting layer of Example 12, dilithium phthalocyanine (C-1), disodium phthalocyanine (C-2), and magnesium phthalocyanine (C-2) were used instead of pyrazabol (P-4). C-4), dipotassium porphyrin (C-7),
5,10,15,20-tetraphenyl-porphine
Magnesium (C-9), 5,10,15,20-tetra (4-pyridyl) -porphine calcium (C-1
0), 4,4,8,8-Tetrakis (1H-pyrazol-1-yl) pyrazabol (P-1) 1,3,5,7-
An organic light-emitting device was produced in the same manner as in Example 12, except that tetramethylpyrazaball (P-3) was used. These devices were evaluated by applying a DC voltage, and the luminous efficiency is shown in (Table 1), and the half-life of luminance when a constant current continuous lighting test at an initial luminance of 300 cd / m 2 is shown in (Table 2).
【０１１３】[0113]
【発明の効果】以上のように本発明の有機発光素子は、
化学的あるいは物理的な安定性を保持しかつ電子の注入
特性に優れた（化１０）As described above, the organic light-emitting device of the present invention comprises:
Excellent chemical or physical stability and excellent electron injection characteristics
【０１１４】[0114]
【化１０】 Embedded image
【０１１５】または（化１１）Or (Formula 11)
【０１１６】[0116]
【化１１】 Embedded image
【０１１７】または（化１２）Or (Formula 12)
【０１１８】[0118]
【化１２】 Embedded image
【０１１９】からなる有機電子注入層を設けることによ
りあるいは電子注入化合物を有機層または有機層の陰極
側に含むことにより、発光効率が向上し、特に寿命特性
に対して飛躍的な効果が得られる。また、本発明の有機
発光素子の製造方法は、化学的あるいは物理的な安定性
を保持しかつ電子の注入特性に優れた（化１０）または
（化１１）または（化１２）からなる有機電子注入層を
設ける工程、あるいは電子注入化合物を有機層または有
機層の陰極側に含有させる工程により、作業性、再現性
に優れ、製造工程の信頼性向上と歩留まり改善の効果を
有するものである。By providing an organic electron injecting layer made of the above or by including an electron injecting compound on the organic layer or on the cathode side of the organic layer, the luminous efficiency is improved, and a dramatic effect is particularly obtained on the life characteristics. . In addition, the method for manufacturing an organic light-emitting device of the present invention provides an organic light-emitting device comprising (Chem. 10) or (Chem. 11) or (Chem. 12), which retains chemical or physical stability and has excellent electron injection characteristics. The step of providing an injection layer or the step of including an electron injection compound on the organic layer or the cathode side of the organic layer is excellent in workability and reproducibility, and has effects of improving the reliability of the manufacturing process and improving the yield.
【図１】有機発光素子の一断面図FIG. 1 is a cross-sectional view of an organic light emitting device.
【図２】電子注入層を積層した有機発光素子の一断面図FIG. 2 is a cross-sectional view of an organic light emitting device having an electron injection layer laminated thereon.
【図３】有機電子注入層を積層した単層型有機発光素子
の一断面図FIG. 3 is a cross-sectional view of a single-layer organic light-emitting device in which an organic electron injection layer is stacked.
【図４】有機電子注入層を積層したＳＨ−Ａ型有機発光
素子の一断面図FIG. 4 is a cross-sectional view of an SH-A type organic light emitting device having an organic electron injection layer laminated thereon.
【図５】有機電子注入層を積層したＳＨ−Ｂ型有機発光
素子の一断面図FIG. 5 is a cross-sectional view of an SH-B type organic light emitting device having an organic electron injection layer laminated thereon.
【図６】有機電子注入層を積層したＤＨ型有機発光素子
の一断面図FIG. 6 is a cross-sectional view of a DH type organic light emitting device having an organic electron injection layer laminated thereon.
【図７】電子注入化合物を含む単層型有機発光素子の一
断面図FIG. 7 is a cross-sectional view of a single-layer organic light-emitting device including an electron injection compound.
【図８】電子注入化合物を含むＳＨ−Ａ型有機発光素子
の一断面図FIG. 8 is a cross-sectional view of an SH-A type organic light emitting device including an electron injection compound.
【図９】電子注入化合物を含むＳＨ−Ｂ型有機発光素子
の一断面図FIG. 9 is a cross-sectional view of an SH-B type organic light emitting device including an electron injection compound.
【図１０】電子注入化合物を含むＤＨ型有機発光素子の
一断面図FIG. 10 is a cross-sectional view of a DH-type organic light emitting device including an electron injection compound.
１ ガラス基板 ２ 透明電極 ３ 陰極 ４ 電子注入層 ５ 電子輸送性発光層 ６ ホール輸送層 ７ 有機発光層 ８ 電子輸送層 ９ 有機電子注入層 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Transparent electrode 3 Cathode 4 Electron injection layer 5 Electron transporting light emitting layer 6 Hole transport layer 7 Organic light emitting layer 8 Electron transport layer 9 Organic electron injection layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉浦 久則 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 久田 均 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 3K007 AB00 AB02 AB03 AB06 AB18 CA01 CA06 CB01 CB03 DA00 DB03 EB00 FA01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hisanori Sugiura 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. Terms (reference) 3K007 AB00 AB02 AB03 AB06 AB18 CA01 CA06 CB01 CB03 DA00 DB03 EB00 FA01
Claims (53)
層と有機電子注入層を有する有機発光素子において、前
記有機電子注入層がアルカリ金属またはアルカリ土類金
属を中心金属に持つ有機金属錯化合物を含むことを特徴
とする有機発光素子。An organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, wherein the organic electron injection layer contains an organic metal complex compound having an alkali metal or an alkaline earth metal as a central metal. An organic light-emitting device comprising:
層と有機電子注入層を有する有機発光素子において、前
記有機電子注入層が下記一般式（化１）を含むことを特
徴とする有機発光素子。 【化１】 （Ｒ１〜Ｒ１２はそれぞれ水素、炭素数１〜６のアルキ
ル基、ハロゲン、炭素数６〜１８のアリール基、窒素原
子を１〜３個含む複素芳香環、ビニル基、アミノ基、シ
アノ基またはチオール基を示し、Ｒ１〜Ｒ１２は互いに
同一であっても異なっていてもよく、Ｒ１とＲ２，Ｒ４
とＲ５，Ｒ７とＲ８，Ｒ１０とＲ１１は互いに結合して
飽和あるいは不飽和の５員環または６員環を形成しても
よく、縮合多環芳香族を形成してもよい。Ｍはアルカリ
金属またはアルカリ土類金属）。2. An organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, wherein the organic electron injection layer comprises the following general formula (1). . Embedded image (R1 to R12 are each hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen, an aryl group having 6 to 18 carbon atoms, a heteroaromatic ring containing 1 to 3 nitrogen atoms, a vinyl group, an amino group, a cyano group or a thiol R1 to R12 may be the same or different from each other, and R1 and R2, R4
And R5, R7 and R8, and R10 and R11 may combine with each other to form a saturated or unsaturated 5- or 6-membered ring, or may form a condensed polycyclic aromatic. M is an alkali metal or an alkaline earth metal).
アニンを含むことを特徴とする請求項２記載の有機発光
素子。3. The organic light emitting device according to claim 2, wherein said organic electron injection layer contains dilithium phthalocyanine.
シアニンを含むことを特徴とする請求項２記載の有機発
光素子。4. The organic light emitting device according to claim 2, wherein said organic electron injection layer contains disodium phthalocyanine.
層と有機電子注入層を有する有機発光素子において、前
記有機電子注入層が下記一般式（化２）を含むことを特
徴とする有機発光素子。 【化２】 （Ｒ１〜Ｒ１２はそれぞれ水素、炭素数１〜６のアルキ
ル基、ハロゲン、炭素数６〜１８のアリール基、窒素原
子を１〜３個含む複素芳香環、ビニル基、アミノ基、シ
アノ基またはチオール基を示し、Ｒ１〜Ｒ１２は互いに
同一であっても異なっていてもよく、Ｒ１とＲ２，Ｒ４
とＲ５，Ｒ７とＲ８，Ｒ１０とＲ１１は互いに結合して
飽和あるいは不飽和の５員環または６員環を形成しても
よく、縮合多環芳香族を形成してもよい。Ｍはアルカリ
金属またはアルカリ土類金属）。5. An organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, wherein the organic electron injection layer contains the following general formula (Formula 2). . Embedded image (R1 to R12 are each hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen, an aryl group having 6 to 18 carbon atoms, a heteroaromatic ring containing 1 to 3 nitrogen atoms, a vinyl group, an amino group, a cyano group or a thiol R1 to R12 may be the same or different from each other, and R1 and R2, R4
And R5, R7 and R8, and R10 and R11 may combine with each other to form a saturated or unsaturated 5- or 6-membered ring, or may form a condensed polycyclic aromatic. M is an alkali metal or an alkaline earth metal).
層と有機電子注入層を有する有機発光素子において、前
記有機電子注入層が電子不足化合物を含むことを特徴と
する有機発光素子。6. An organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, wherein the organic electron injection layer contains an electron deficient compound.
であることを特徴とする請求項６記載の有機発光素子。 【化３】 （Ｒ１及びＲ２は少なくとも２つの窒素原子を含む含窒
素芳香環もしくは含窒素芳香環誘導体を有する架橋配位
子あるいはハロゲン、炭素数１〜３のアルキルを有する
架橋配位子であり、含窒素芳香環中の窒素を配位原子と
する。Ｒ３，Ｒ４，Ｒ５およびＲ６はそれぞれ水素、ア
ルキル、アリール、アリール誘導体及び少なくとも１つ
の窒素原子を含む含窒素芳香環もしくは含窒素芳香環誘
導体から選ばれる１つであり、Ｍは中心金属）。7. The method according to claim 1, wherein the electron deficient compound is represented by the following general formula (3).
The organic light-emitting device according to claim 6, wherein Embedded image (R1 and R2 are a bridging ligand having a nitrogen-containing aromatic ring or a nitrogen-containing aromatic ring derivative containing at least two nitrogen atoms or a bridging ligand having a halogen or an alkyl having 1 to 3 carbon atoms. R3, R4, R5 and R6 are each selected from hydrogen, alkyl, aryl, aryl derivatives and nitrogen-containing aromatic rings or nitrogen-containing aromatic ring derivatives containing at least one nitrogen atom. And M is the central metal).
を有することを特徴とする請求項６記載の有機発光素
子。8. The organic light emitting device according to claim 6, wherein said electron deficient compound has a pyrazaball structure.
テトラキス（１Ｈ−ピラゾールー１−イル）ピラザボー
ルであることを特徴とする請求項６記載の有機発光素
子。9. The method according to claim 9, wherein the electron-deficient compound is 4,4,8,8-
The organic light-emitting device according to claim 6, wherein the organic light-emitting device is a tetrakis (1H-pyrazol-1-yl) pyrazaball.
ｎｍであることを特徴とする請求項１〜９のいずれかに
記載の有機発光素子。10. The organic electron injection layer having a thickness of 0.2 to 2
The organic light-emitting device according to any one of claims 1 to 9, wherein
ることを特徴とする請求項１〜１０のいずれかに記載の
有機発光素子。11. The organic light emitting device according to claim 1, wherein the layer between the anode and the cathode comprises an organic light emitting layer.
機発光層の積層構成であることを特徴とする請求項１〜
１０のいずれかに記載の有機発光素子。12. The method according to claim 1, wherein the layer between the anode and the cathode has a laminated structure of a hole transport layer and an organic light emitting layer.
11. The organic light-emitting device according to any one of 10).
輸送層の積層構成であることを特徴とする請求項１〜１
０のいずれかに記載の有機発光素子。13. The method according to claim 1, wherein the layer between the anode and the cathode has a laminated structure of an organic light emitting layer and an electron transport layer.
0. The organic light emitting device according to any one of 1.
機発光層と電子輸送層の積層構成であることを特徴とす
る請求項１〜１０のいずれかに記載の有機発光素子。14. The organic light emitting device according to claim 1, wherein the layer between the anode and the cathode has a laminated structure of a hole transport layer, an organic light emitting layer, and an electron transport layer.
光層を有する有機発光素子において、有機層にアルカリ
金属またはアルカリ土類金属を中心金属に持つ有機金属
錯化合物からなる電子注入化合物を含むことを特徴とす
る有機発光素子。15. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic layer contains an electron injecting compound comprising an organometallic complex compound having an alkali metal or an alkaline earth metal as a central metal. Organic light-emitting device characterized by the following.
光層を有する有機発光素子において、有機層に一般式
（化１）からなる電子注入化合物を含むことを特徴とす
る有機発光素子。16. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic layer contains an electron injecting compound represented by the general formula (1).
シアニンであることを特徴とする請求項１６記載の有機
発光素子。17. The organic light emitting device according to claim 16, wherein said electron injection compound is dilithium phthalocyanine.
ロシアニンであることを特徴とする請求項１６記載の有
機発光素子。18. The organic light emitting device according to claim 16, wherein said electron injection compound is disodium phthalocyanine.
光層を有する有機発光素子において、有機層に一般式
（化２）からなる電子注入化合物を含むことを特徴とす
る有機発光素子。19. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic layer contains an electron injection compound represented by the general formula (Formula 2).
光層を有する有機発光素子において、有機層に電子不足
化合物からなる電子注入化合物を含むことを特徴とする
有機発光素子。20. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic layer contains an electron injecting compound comprising an electron deficient compound.
あることを特徴とする請求項２０記載の有機発光素子。21. The organic light emitting device according to claim 20, wherein said electron deficient compound is represented by the general formula (3).
造を有することを特徴とする請求項２０記載の有機発光
素子。22. The organic light-emitting device according to claim 20, wherein the electron-deficient compound has a pyrazaball structure.
−テトラキス（１Ｈ−ピラゾールー１−イル）ピラザボ
ールであることを特徴とする請求項２０記載の有機発光
素子。23. The method according to claim 23, wherein the electron-deficient compound is 4,4,8,8.
The organic light-emitting device according to claim 20, wherein the organic light-emitting device is -tetrakis (1H-pyrazol-1-yl) pyrazaball.
光層を有する有機発光素子において、有機層の陰極側に
アルカリ金属またはアルカリ土類金属を中心金属に持つ
有機金属錯化合物からなる電子注入化合物を含むことを
特徴とする有機発光素子。24. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein an electron injecting compound comprising an organometallic complex compound having an alkali metal or an alkaline earth metal as a central metal is provided on the cathode side of the organic layer. An organic light-emitting device comprising:
光層を有する有機発光素子において、有機層の陰極側に
一般式（化１）からなる電子注入化合物を含むことを特
徴とする有機発光素子。25. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic light emitting device comprises an electron injecting compound represented by the general formula (1) on the cathode side of the organic layer.
シアニンであることを特徴とする請求項２５記載の有機
発光素子。26. The organic light emitting device according to claim 25, wherein said electron injection compound is dilithium phthalocyanine.
ロシアニンであることを特徴とする請求項２５記載の有
機発光素子。27. The organic light emitting device according to claim 25, wherein said electron injecting compound is disodium phthalocyanine.
光層を有する有機発光素子において、有機層の陰極側に
一般式（化２）からなる電子注入化合物を含むことを特
徴とする有機発光素子。28. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic light emitting device comprises an electron injecting compound represented by the general formula (2) on the cathode side of the organic layer.
光層を有する有機発光素子において、有機層の陰極側に
電子不足化合物からなる電子注入化合物を含むことを特
徴とする有機発光素子。29. An organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic light emitting device comprises an electron injecting compound comprising an electron deficient compound on the cathode side of the organic layer.
あることを特徴とする請求項２９記載の有機発光素子。30. The organic light-emitting device according to claim 29, wherein the electron-deficient compound is represented by the general formula (Formula 3).
造を有することを特徴とする請求項２９記載の有機発光
素子。31. The organic light emitting device according to claim 29, wherein said electron deficient compound has a pyrazaball structure.
−テトラキス（１Ｈ−ピラゾールー１−イル）ピラザボ
ールであることを特徴とする請求項２９記載の有機発光
素子。32. The electron-deficient compound is 4,4,8,8
30. The organic light-emitting device according to claim 29, wherein the organic light-emitting device is -tetrakis (1H-pyrazol-1-yl) pyrazaball.
電子注入化合物を均一に含むことを特徴とする請求項１
５〜３２のいずれかに記載の有機発光素子。33. The method according to claim 1, wherein the electron injecting compound is uniformly contained in the organic layer or on the cathode side of the organic layer.
The organic light-emitting device according to any one of claims 5 to 32.
電子注入化合物を、陰極に近接するほど高濃度になるよ
うに濃度勾配をつけて含むことを特徴とする請求項１５
〜３２のいずれかに記載の有機発光素子。34. The method according to claim 15, wherein the electron injecting compound is contained in the organic layer or on the cathode side of the organic layer with a concentration gradient such that the concentration becomes higher as the cathode is closer to the cathode.
33. The organic light-emitting device according to any one of items 32 to 32.
とする請求項１５〜３２のいずれかに記載の有機発光素
子。35. The organic light emitting device according to claim 15, wherein the organic layer comprises an organic light emitting layer.
層構成であり、電子注入化合物を含む層が有機発光層で
あることを特徴とする請求項１５〜３２のいずれかに記
載の有機発光素子。36. The organic light-emitting device according to claim 15, wherein the organic layer has a laminated structure of a hole transport layer and an organic light-emitting layer, and the layer containing an electron injection compound is an organic light-emitting layer. Light emitting element.
構成であり、電子注入化合物を含む層が電子輸送層であ
ることを特徴とする請求項１５〜３２のいずれかに記載
の有機発光素子。37. The organic compound according to claim 15, wherein the organic layer has a laminated structure of an organic light emitting layer and an electron transport layer, and the layer containing an electron injecting compound is an electron transport layer. Light emitting element.
子輸送層の積層構成であり、電子注入化合物を含む層が
電子輸送層であることを特徴とする請求項１５〜３２の
いすれかに記載の有機発光素子。38. The method according to claim 15, wherein the organic layer has a laminated structure of a hole transporting layer, an organic light emitting layer, and an electron transporting layer, and the layer containing the electron injecting compound is an electron transporting layer. An organic light-emitting device according to any of the above items
属からなることを特徴とする請求項１〜３８のいずれか
に記載の有機発光素子。39. The organic light-emitting device according to claim 1, wherein the cathode is made of a metal having a work function of 4.0 eV or more.
ちのいずれかであることを特徴とする請求項１〜３８の
いずれかに記載の有機発光素子。40. The organic light-emitting device according to claim 1, wherein the cathode is any one of Al, Ag, In, and Bi.
光層と有機電子注入層を有する有機発光素子の製造方法
において、前記有機電子注入層をアルカリ金属またはア
ルカリ土類金属を中心金属に持つ有機金属錯化合物から
形成することを特徴とする有機発光素子の製造方法。41. A method of manufacturing an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, wherein the organic electron injection layer has an alkali metal or an alkaline earth metal as a central metal. A method for producing an organic light emitting device, wherein the method is formed from a complex compound.
光層と有機電子注入層を有する有機発光素子の製造方法
において、前記有機電子注入層を一般式（化１）から形
成することを特徴とする有機発光素子の製造方法。42. A method of manufacturing an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, wherein the organic electron injection layer is formed by the general formula (1). A method for manufacturing an organic light emitting device.
光層と有機電子注入層を有する有機発光素子の製造方法
において、前記有機電子注入層を一般式（化２）から形
成することを特徴とする有機発光素子の製造方法。43. A method of manufacturing an organic light-emitting device having at least an organic light-emitting layer and an organic electron-injection layer between an anode and a cathode, wherein the organic electron-injection layer is formed by the general formula (2). A method for manufacturing an organic light emitting device.
光層と有機電子注入層を有する有機発光素子の製造方法
において、前記有機電子注入層を電子不足化合物から形
成することを特徴とする有機発光素子の製造方法。44. A method of manufacturing an organic light emitting device having at least an organic light emitting layer and an organic electron injection layer between an anode and a cathode, wherein the organic electron injection layer is formed from an electron deficient compound. Manufacturing method.
光層を有する有機発光素子の製造方法において、有機層
あるいは有機層の陰極側に、アルカリ金属またはアルカ
リ土類金属を中心金属に持つ有機金属錯化合物からなる
電子注入化合物を含有させることを特徴とする有機発光
素子の製造方法。45. A method for producing an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein an organic metal complex having an alkali metal or an alkaline earth metal as a central metal is provided on the organic layer or on the cathode side of the organic layer. A method for producing an organic light emitting device, comprising an electron injection compound comprising a compound.
光層を有する有機発光素子の製造方法において、有機層
あるいは有機層の陰極側に一般式（化１）からなる電子
注入化合物を含有させることを特徴とする有機発光素子
の製造方法。46. A method of manufacturing an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic layer or the cathode side of the organic layer contains an electron injecting compound represented by the general formula (1). A method for manufacturing an organic light emitting device, which is characterized in that:
光層を有する有機発光素子の製造方法において、有機層
あるいは有機層の陰極側に一般式（化２）からなる電子
注入化合物を含有させることを特徴とする有機発光素子
の製造方法。47. A method for producing an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, wherein the organic layer or the cathode side of the organic layer contains an electron injecting compound represented by the general formula (2). A method for manufacturing an organic light emitting device, which is characterized in that:
光層を有する有機発光素子の製造方法において、有機層
あるいは有機層の陰極側に電子不足化合物からなる電子
注入化合物を含有させることを特徴とする有機発光素子
の製造方法。48. A method of manufacturing an organic light emitting device having at least an organic light emitting layer between an anode and a cathode, characterized in that an electron injecting compound comprising an electron deficient compound is contained in the organic layer or the cathode side of the organic layer. A method for manufacturing an organic light emitting device.
アニンから形成することを特徴とする請求項４２または
４６記載の有機発光素子の製造方法。49. The method according to claim 42, wherein the electron injection layer is formed from dilithium phthalocyanine.
シアニンから形成することを特徴とする請求項４２また
は４６記載の有機発光素子の製造方法。50. The method according to claim 42, wherein the electron injection layer is formed of disodium phthalocyanine.
であることを特徴とする請求項４４または４８記載の有
機発光素子の製造方法。51. The electron-deficient compound represented by the general formula (3)
49. The method for manufacturing an organic light emitting device according to claim 44, wherein:
造を有することを特徴とする請求項４４または４８記載
の有機発光素子の製造方法。52. The method according to claim 44, wherein the electron-deficient compound has a pyrazaball structure.
−テトラキス（１Ｈ−ピラゾールー１−イル）ピラザボ
ールであることを特徴とする請求項４４または４８記載
の有機発光素子の製造方法。53. The method according to claim 53, wherein the electron-deficient compound is 4,4,8,8.
49. The method for producing an organic light-emitting device according to claim 44, wherein the method is -tetrakis (1H-pyrazol-1-yl) pyrazaball.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11214712A JP2001043973A (en) | 1999-07-29 | 1999-07-29 | Organic luminescent element and manufacture of the same |
| US09/495,654 US6391482B1 (en) | 1999-02-04 | 2000-02-01 | Organic material for electroluminescent device and electroluminescent device using the same |
| DE60000455T DE60000455T2 (en) | 1999-02-04 | 2000-02-02 | Organic material for electroluminescent device and electroluminescent device |
| EP00102058A EP1026222B1 (en) | 1999-02-04 | 2000-02-02 | Organic material for electroluminescent device and electroluminescent device using the same |
| KR10-2000-0005505A KR100360204B1 (en) | 1999-02-04 | 2000-02-03 | Organic Material For Electro-luminescent Device And Electro-luminescent Device Using The Same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11214712A JP2001043973A (en) | 1999-07-29 | 1999-07-29 | Organic luminescent element and manufacture of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001043973A true JP2001043973A (en) | 2001-02-16 |
Family
ID=16660377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11214712A Pending JP2001043973A (en) | 1999-02-04 | 1999-07-29 | Organic luminescent element and manufacture of the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001043973A (en) |
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| JPH11345687A (en) * | 1998-06-01 | 1999-12-14 | Canon Inc | Luminescent element |
| WO2001052606A1 (en) * | 2000-01-13 | 2001-07-19 | Matsushita Electric Industrial Co., Ltd. | Electrode body, thin-film el device comprising the same, method for manufacturing the same, and display and illuminator comprising the thin-film el device |
| JP2002280184A (en) * | 2001-03-16 | 2002-09-27 | Nippon Seiki Co Ltd | Organic electroluminescent element |
| JP2003045671A (en) * | 2001-05-22 | 2003-02-14 | Semiconductor Energy Lab Co Ltd | Light emitting device and its manufacturing method |
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- 1999-07-29 JP JP11214712A patent/JP2001043973A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11345687A (en) * | 1998-06-01 | 1999-12-14 | Canon Inc | Luminescent element |
| US6849346B2 (en) | 2000-01-13 | 2005-02-01 | Matsushita Electric Industrial Co., Ltd. | Electrode and thin film EL device including the same and methods of fabricating the same and display device and lighting system including the thin film EL device |
| WO2001052606A1 (en) * | 2000-01-13 | 2001-07-19 | Matsushita Electric Industrial Co., Ltd. | Electrode body, thin-film el device comprising the same, method for manufacturing the same, and display and illuminator comprising the thin-film el device |
| JP2002280184A (en) * | 2001-03-16 | 2002-09-27 | Nippon Seiki Co Ltd | Organic electroluminescent element |
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| JP2003045671A (en) * | 2001-05-22 | 2003-02-14 | Semiconductor Energy Lab Co Ltd | Light emitting device and its manufacturing method |
| US8450741B2 (en) | 2001-05-22 | 2013-05-28 | Semiconductor Energy Laboratory Co., Ltd. | Luminescent device and process of manufacturing the same |
| US10103211B2 (en) | 2001-05-22 | 2018-10-16 | Semiconductor Energy Laboratory Co., Ltd. | Luminescent device having light-emitting element and transistor |
| US8803152B2 (en) | 2001-05-22 | 2014-08-12 | Semiconductor Energy Laboratory Co., Ltd. | Luminescent device and process of manufacturing the same |
| US9761645B2 (en) | 2001-05-22 | 2017-09-12 | Semiconductor Energy Laboratory Co., Ltd. | Luminescent device having light emitting element and transistor |
| JP2006093628A (en) * | 2004-09-27 | 2006-04-06 | Hodogaya Chem Co Ltd | Organic semiconductor laser device |
| JP2012023388A (en) * | 2005-02-16 | 2012-02-02 | Massachusetts Inst Of Technol <Mit> | Light emitting devices including semiconductor nanocrystals |
| US8945725B2 (en) | 2009-08-31 | 2015-02-03 | Udc Ireland Limited | Organic electroluminescence device |
| US10403832B2 (en) | 2009-08-31 | 2019-09-03 | Udc Ireland Limited | Organic electroluminescence device |
| US11832508B2 (en) | 2009-08-31 | 2023-11-28 | Udc Ireland Limited | Organic electroluminescence device |
| JP2014013945A (en) * | 2013-10-24 | 2014-01-23 | Udc Ireland Ltd | Organic electroluminescent element |
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