JP2001196179A - Organic el element - Google Patents
Organic el elementInfo
- Publication number
- JP2001196179A JP2001196179A JP2000002697A JP2000002697A JP2001196179A JP 2001196179 A JP2001196179 A JP 2001196179A JP 2000002697 A JP2000002697 A JP 2000002697A JP 2000002697 A JP2000002697 A JP 2000002697A JP 2001196179 A JP2001196179 A JP 2001196179A
- Authority
- JP
- Japan
- Prior art keywords
- group
- organic
- layer
- transport layer
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims description 56
- 239000007924 injection Substances 0.000 claims description 56
- 239000000126 substance Substances 0.000 claims description 25
- BRSRUYVJULRMRQ-UHFFFAOYSA-N 1-phenylanthracene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 BRSRUYVJULRMRQ-UHFFFAOYSA-N 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000004104 aryloxy group Chemical group 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 230000006698 induction Effects 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 131
- 150000001875 compounds Chemical class 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000758 substrate Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- -1 phenylanthryl group Chemical group 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- MGRRGKWPEVFJSH-UHFFFAOYSA-N 10-(10-oxoanthracen-9-ylidene)anthracen-9-one Chemical compound C12=CC=CC=C2C(=O)C2=CC=CC=C2C1=C1C2=CC=CC=C2C(=O)C2=CC=CC=C21 MGRRGKWPEVFJSH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 2
- PLMFIWDPKYXMGE-UHFFFAOYSA-N 2-chloro-9,10-diphenylanthracene Chemical compound C=12C=CC=CC2=C(C=2C=CC=CC=2)C2=CC(Cl)=CC=C2C=1C1=CC=CC=C1 PLMFIWDPKYXMGE-UHFFFAOYSA-N 0.000 description 2
- OEYLQYLOSLLBTR-UHFFFAOYSA-N 9-(2-phenylphenyl)-10-[10-(2-phenylphenyl)anthracen-9-yl]anthracene Chemical group C1=CC=CC=C1C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1C1=CC=CC=C1 OEYLQYLOSLLBTR-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HLSPEMVMBBEBBJ-UHFFFAOYSA-N [Li]C1=CC=CC=C1C1=CC=CC=C1 Chemical group [Li]C1=CC=CC=C1C1=CC=CC=C1 HLSPEMVMBBEBBJ-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 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 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- ZKSVYBRJSMBDMV-UHFFFAOYSA-N 1,3-diphenyl-2-benzofuran Chemical compound C1=CC=CC=C1C1=C2C=CC=CC2=C(C=2C=CC=CC=2)O1 ZKSVYBRJSMBDMV-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- OBZZEGPFTUQMCZ-UHFFFAOYSA-N 1-phenyl-10h-anthracen-9-one Chemical compound C=12C(=O)C3=CC=CC=C3CC2=CC=CC=1C1=CC=CC=C1 OBZZEGPFTUQMCZ-UHFFFAOYSA-N 0.000 description 1
- MVWPVABZQQJTPL-UHFFFAOYSA-N 2,3-diphenylcyclohexa-2,5-diene-1,4-dione Chemical class O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVWPVABZQQJTPL-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- DKLTXNUAWUJUGS-UHFFFAOYSA-N 4-(4-aminophenyl)-3-[4-(N-(4-methylphenyl)anilino)phenyl]aniline Chemical compound CC1=CC=C(C=C1)N(C1=CC=C(C=C1)C1=C(C=CC(=C1)N)C1=CC=C(C=C1)N)C1=CC=CC=C1 DKLTXNUAWUJUGS-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 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 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、平面ディスプレイ又は
平面光源等に用いられる有機化合物を用いた電界発光素
子（有機ＥＬ素子）に関するもので、詳しくは、有機化
合物からなる積層構造薄膜に電界を印加して光を放出す
る素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroluminescent device (organic EL device) using an organic compound used for a flat display or a flat light source. The present invention relates to an element that emits light when applied.
【０００２】[0002]
【従来の技術】有機ＥＬ素子は、蛍光性有機化合物を含
む薄膜を、陰極と陽極とで挟んだ構成を有し、前記薄膜
に電子およびホールを注入して再結合させることにより
励起子（エキシトン）を生成させ、このエキシトンが失
活する際の光の放出（蛍光・燐光）を利用して発光する
素子である。2. Description of the Related Art An organic EL device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between a cathode and an anode, and electrons and holes are injected into the thin film and recombined to form excitons. ), And emits light by utilizing light emission (fluorescence / phosphorescence) when the exciton is deactivated.
【０００３】有機ＥＬ素子の特徴は、１０V 程度の低電
圧で１００〜１００００cd/m2 程度の高輝度の面発光が
可能であり、また蛍光物質の種類を選択することにより
青色から赤色までの発光が可能なことであるが、発光寿
命が短く、保存耐久性に劣るという問題点を有してお
り、これらの問題点を解消するために現在様々な研究、
開発が進められているのが現状である。[0003] The features of the organic EL element are that it can emit a high-luminance surface light of about 100 to 10000 cd / m 2 at a low voltage of about 10 V, and emit light from blue to red by selecting the type of fluorescent substance. Although it is possible, there is a problem that the luminescent life is short, and the storage durability is inferior, and various studies are currently being conducted to solve these problems.
It is currently being developed.
【０００４】具体的には、高効率、長寿命化の手段とし
て、蛍光量子収率の大きい蛍光性色素を少量ドーピング
する方法（特開平05-198377号公報、特開平07-135077号
公報等）、また、発光層としてホール輸送性材料と電子
輸送性材料を混合したバイポーラ型発光層を用い、キャ
リアの再結合領域を拡大し、再結合確率を向上させて高
効率素子を得る方法（ WO 98/0836号、特開平03-114197
号公報等）等が報告されている。Specifically, a method of doping a small amount of a fluorescent dye having a high fluorescence quantum yield as a means for increasing the efficiency and elongating the lifetime (Japanese Patent Laid-Open Nos. 05-198377 and 07-135077). Further, a method of obtaining a highly efficient device by using a bipolar light emitting layer in which a hole transporting material and an electron transporting material are mixed as a light emitting layer, expanding a carrier recombination region and improving a recombination probability (WO 98 / 0836, JP 03-114197A
And other publications have been reported.
【０００５】しかしながら、ドーピング法を用いる場
合、ドーパントとなる蛍光性色素の多くは濃度消光性が
強く、素子を作成する際は重量比にして数パーセントの
レベルでのドーパント濃度の制御が必要となる。一般的
に低分子化合物を用いたＥＬ素子は真空蒸着法で作成さ
れることが多く、このような精密な濃度制御を行うこと
は容易ではなく、製造マージンを狭くする原因となって
いる。さらに、ドーピングにより青い発光を得るために
はエネルギーギャップの大きなドーパントを発光させる
ため、ホストとなり得る材料は限定され、ドーパントの
組み合わせの選定は困難となる。However, when the doping method is used, most of the fluorescent dyes serving as dopants have a strong concentration quenching property, and it is necessary to control the dopant concentration at a level of several percent by weight when fabricating the device. . Generally, an EL element using a low-molecular compound is often prepared by a vacuum evaporation method, and it is not easy to perform such precise concentration control, which causes a narrowing of a manufacturing margin. Further, in order to obtain blue light emission by doping, a dopant having a large energy gap is caused to emit light, so that a material that can serve as a host is limited, and it is difficult to select a combination of dopants.
【０００６】また、バイポーラ型発光層を用いた場合で
も再結合確率は向上するものの、最終的にエネルギーを
光として取り出すためには高い蛍光量子収率を有するド
ーパントの使用が必要となる場合が多い。しかも、この
ようなバイポーラ型の混合発光層を用いると、駆動電圧
は比較的高くなってしまうという難点がある。Although the recombination probability is improved even when a bipolar light emitting layer is used, it is often necessary to use a dopant having a high fluorescence quantum yield in order to finally extract energy as light. . In addition, when such a bipolar mixed light emitting layer is used, there is a problem that the driving voltage is relatively high.
【０００７】一方、本発明者らは、特開平08-12600号公
報で、物理的変化、光化学的変化、電気化学的変化の少
ないフェニルアントラセン誘導体を用いた高輝度発光素
子を開示しているが、視感度の低い青色の領域に関して
は、十分な効率が得られておらず、また、発光寿命、耐
久性の面でも実用に向けてさらなる特性の向上が必要と
されている。On the other hand, the present inventors have disclosed in JP-A-08-12600 a high-luminance light-emitting device using a phenylanthracene derivative having little physical change, photochemical change and electrochemical change. In the blue region having low luminosity, sufficient efficiency has not been obtained, and further improvement is required in terms of luminous life and durability for practical use.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、青色
の領域において低濃度での精密なドーピングを行うこと
なく混合発光層のみで十分な効率と、実用に耐えうる発
光寿命、さらには広い製造マージンを持ち、しかも、バ
イポーラ型混合層を用いたＥＬ素子に比べると駆動電圧
を低く抑えることの可能な有機ＥＬ素子を実現すること
である。SUMMARY OF THE INVENTION An object of the present invention is to provide a light-emitting layer having sufficient efficiency, practically usable light-emitting life, and a broader light-emitting layer without the need for precise doping at a low concentration in the blue region. It is an object of the present invention to provide an organic EL device having a manufacturing margin and capable of suppressing a driving voltage lower than that of an EL device using a bipolar mixed layer.
【０００９】[0009]
【課題を解決するための手段】このような目的は、下記
（１）〜（９）の本発明により達成される。 （１） 下記化５で表されるフェニルアントラセン誘導
体と下記化６で表されるフェニルアントラセン誘導体の
それぞれ少なくとも一種以上を同時に含有する、少なく
とも１層の有機化合物混合層を有する有機ＥＬ素子。This and other objects are achieved by the present invention which is defined below as (1) to (9). (1) An organic EL device having at least one organic compound mixed layer simultaneously containing at least one or more of a phenylanthracene derivative represented by the following formula (5) and a phenylanthracene derivative represented by the following formula (6).
【００１０】[0010]
【化５】 Embedded image
【００１１】[0011]
【化６】 Embedded image
【００１２】〔化５において、Ｒ1 およびＲ2 は、各々
アルキル基、シクロアルキル基、アリール基、アルケニ
ル基、アルコキシ基、アリーロキシ基、アミノ基または
複素環基を表し、これらは同一でも異なるものであって
もよい。ｒ１およびｒ２は、各々、０または１〜５の整
数を表す。ｒ１およびｒ２が、各々、２以上の整数であ
るとき、Ｒ1 同士およびＲ2 同士は各々同一でも異なる
ものであってもよく、Ｒ 1 同士またはＲ2 同士は結合し
て環を形成してもよい。化６において、Ｒ3 およびＲ4
は、各々アルキル基、シクロアルキル基、アリール基、
アルケニル基、アルコキシ基、アリーロキシ基、アミノ
基または複素環基を表し、これらは同一でも異なるもの
であってもよい。ｒ３およびｒ４は、各々、０または１
〜５の整数を表す。ｒ３およびｒ４が、各々、２以上の
整数であるとき、Ｒ3 同士およびＲ4 同士は各々同一で
も異なるものであってもよく、Ｒ 3 同士またはＲ4 同士
は結合して環を形成してもよい。〕 （２） 下記化７で表されるフェニルアントラセン誘導
体と下記化８で表されるフェニルアントラセン誘導体の
それぞれ少なくとも一種以上を同時に含有する、少なく
とも１層の有機化合物混合層を有する有機ＥＬ素子。In the chemical formula 5, R1 And RTwo Are each
Alkyl group, cycloalkyl group, aryl group, alkenyl
Group, alkoxy group, aryloxy group, amino group or
Represents a heterocyclic group, which may be the same or different,
Is also good. r1 and r2 are each 0 or an integer of 1 to 5;
Represents a number. r1 and r2 are each an integer of 2 or more
When R1 Each other and RTwo Each other is the same or different
May be R 1 Each other or RTwo Join together
To form a ring. In the chemical formula 6, RThree And RFour
Is an alkyl group, a cycloalkyl group, an aryl group,
Alkenyl group, alkoxy group, aryloxy group, amino
Groups or heterocyclic groups, which are the same or different
It may be. r3 and r4 are each 0 or 1
Represents an integer of from 5 to 5. r3 and r4 are each 2 or more
When an integer, RThree Each other and RFour Each other is the same
May also be different, R Three Each other or RFour Each other
May combine to form a ring. (2) Phenylanthracene derivative represented by the following formula (7):
Of the phenylanthracene derivative represented by the following formula:
Each containing at least one or more at the same time, less
Both are organic EL devices having one organic compound mixed layer.
【００１３】[0013]
【化７】 Embedded image
【００１４】[0014]
【化８】 Embedded image
【００１５】〔化７において、Ｒ51 およびＲ52 は、各
々アルキル基、シクロアルキル基、アリール基、アルケ
ニル基、アルコキシ基、アリーロキシ基、アミノ基また
は複素環基を表し、これらは同一でも異なるものであっ
てもよい。化８において、Ｒ53 およびＲ54 は、各々ア
ルキル基、シクロアルキル基、アリール基、アルケニル
基、アルコキシ基、アリーロキシ基、アミノ基または複
素環基を表し、これらは同一でも異なるものであっても
よい。 〕 （３） 前記化５および化６におけるＲ1 、Ｒ2 、Ｒ3
およびＲ4 がアリール基である上記（１）の有機ＥＬ素
子。 （４） 前記化７および化８におけるＲ51 、Ｒ52 、Ｒ
53 およびＲ54 がアリール基である上記（２）の有機Ｅ
Ｌ素子。 （５） 前記化５で表されるフェニルアントラセン誘導
体と化６で表されるフェニルアントラセン誘導体とをそ
れぞれ９５：５〜２０：８０wt％含有する上記（１）ま
たは（３）の有機ＥＬ素子。 （６） 前記化７で表されるフェニルアントラセン誘導
体と化８で表されるフェニルアントラセン誘導体とをそ
れぞれ９５：５〜２０：８０wt％含有する上記（２）ま
たは（４）の有機ＥＬ素子。 （７） 前記有機化合物混合層が発光層である上記
（１）〜（６）のいずれかの有機ＥＬ素子。 （８） さらに、少なくとも１層のホール注入層と、少
なくとも１層のホール輸送層と、少なくとも１層の電子
注入輸送層とを有する上記（１）〜（７）のいずれかの
有機ＥＬ素子。 （９） さらに、少なくとも１層のホール注入層と、少
なくとも１層のホール輸送層と、少なくとも１層の電子
輸送層と、少なくとも１層の電子注入層とを有する上記
（１）〜（８）のいずれかの有機ＥＬ素子。Wherein R 51 and R 52 each represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, which are the same or different. It may be. In Chemical Formula 8, R 53 and R 54 each represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, and these may be the same or different. Good. (3) R 1 , R 2 , R 3 in Chemical formulas 5 and 6
And the organic EL device according to the above (1), wherein R 4 is an aryl group. (4) R 51 , R 52 and R in the above formulas 7 and 8
The organic E of the above (2), wherein 53 and R 54 are aryl groups.
L element. (5) The organic EL device according to the above (1) or (3), containing 95: 5 to 20:80 wt% of the phenylanthracene derivative represented by the above formula 5 and the phenylanthracene derivative represented by the following formula 6 respectively. (6) The organic EL device according to the above (2) or (4), containing 95: 5 to 20:80 wt% of the phenylanthracene derivative represented by the formula 7 and the phenylanthracene derivative represented by the formula 8 respectively. (7) The organic EL device according to any one of (1) to (6), wherein the organic compound mixed layer is a light emitting layer. (8) The organic EL device according to any one of (1) to (7), further including at least one hole injection layer, at least one hole transport layer, and at least one electron injection transport layer. (9) The above (1) to (8) further including at least one hole injection layer, at least one hole transport layer, at least one electron transport layer, and at least one electron injection layer. Any one of the organic EL devices.
【００１６】[0016]
【作用】本発明の有機ＥＬ素子は上記化５および上記化
６のフェニルアントラセン誘導体を同時に発光層に用い
るため、１０mA／cm2の電流密度において最大で ６５
０cd／m2 以上の輝度が得られ、このときの駆動電圧は
６V程度と低電圧である。さらに、７５０mA／cm2 程度
の電流密度では３００００cd／m2 の輝度が安定して得
られる。５０mA／cm2 で駆動した際には、初期輝度３０
００cd／m2 以上において半減時間３００時間と長寿命
である。[Action] The organic EL device of the present invention is for use in simultaneously emitting layer phenyl anthracene derivative of the formula 5 and the reduction 6 with a maximum at a current density of 10 mA / cm 2 65
A luminance of 0 cd / m 2 or more is obtained, and the driving voltage at this time is as low as about 6 V. Further, at a current density of about 750 mA / cm 2, a luminance of 30,000 cd / m 2 can be stably obtained. When driven at 50 mA / cm 2 , the initial luminance is 30
At a time of 00 cd / m 2 or more, the half life is 300 hours, which is a long life.
【００１７】また、本発明の混合層を発光層とする場
合、発光層材料の結晶化が抑制され、また発光層のキャ
リアトラップ性を向上させることができる。混合比は、
２種の化合物を混合する場合、ほぼ１：１の場合が効
率、寿命ともに最大となるが、混合比が４：１または
１：４程度の場合でも効率の減少は小さく１割程度であ
り、さらに９５：５の場合でも１５％程度であり、従来
のドーピング法とは異なり非常に広い製造マージンを有
している。When the mixed layer of the present invention is used as a light emitting layer, crystallization of the light emitting layer material can be suppressed, and the carrier trapping property of the light emitting layer can be improved. The mixing ratio is
When two kinds of compounds are mixed, the efficiency and life are maximized when the ratio is approximately 1: 1. However, even when the mixing ratio is about 4: 1 or 1: 4, the decrease in efficiency is small and about 10%. Furthermore, even in the case of 95: 5, it is about 15%, which has a very wide manufacturing margin unlike the conventional doping method.
【００１８】[0018]
【具体的構成】以下、本発明の具体的構成について詳細
に説明する。本発明の有機ＥＬ素子の発光層に用いられ
るフェニルアントラセン誘導体は化５および化６で示さ
れるものである。化５について説明すると、Ｒ1 および
Ｒ2は、各々アルキル基、シクロアルキル基、アリール
基、アルケニル基、アルコキシ基、アリーロキシ基、ア
ミノ基または複素環基を表す。[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail. The phenylanthracene derivative used in the light emitting layer of the organic EL device of the present invention is represented by the following formulas (5) and (6). Explaining Chemical formula 5, R 1 and R 2 each represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group.
【００１９】Ｒ1 、Ｒ2 で表されるアルキル基として
は、直鎖状でも分岐を有するものであってもよく、炭素
数１〜１０、さらには１〜４の置換もしくは無置換のア
ルキル基が好ましい。特に、炭素数１〜４の無置換のア
ルキル基が好ましく、具体的にはメチル基、エチル基、
（ｎ−，ｉ−）プロピル基、（ｎ−，ｉ−，ｓ−，ｔ
−）ブチル基等が挙げられる。The alkyl group represented by R 1 and R 2 may be linear or branched, and may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or 1 to 4 carbon atoms. Is preferred. In particular, an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group,
(N-, i-) propyl group, (n-, i-, s-, t
-) Butyl group and the like.
【００２０】Ｒ1 、Ｒ2 で表されるシクロアルキル基と
しては、シクロヘキシル基、シクロペンチル基等が挙げ
られる。Examples of the cycloalkyl group represented by R 1 and R 2 include a cyclohexyl group and a cyclopentyl group.
【００２１】Ｒ1 、Ｒ2 で表されるアリール基として
は、炭素数６〜２０のものが好ましく、さらにはフェニ
ル基、トリル基等の置換基を有するものであってもよ
い。具体的には、フェニル基、（ｏ−，ｍ−，ｐ−）ト
リル基、ピレニル基、ナフチル基、アントリル基、ビフ
ェニル基、フェニルアントリル基、トリルアントリル基
等が挙げられる。The aryl group represented by R 1 and R 2 preferably has 6 to 20 carbon atoms, and may further have a substituent such as a phenyl group or a tolyl group. Specific examples include a phenyl group, an (o-, m-, p-) tolyl group, a pyrenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenylanthryl group, and a tolyl anthryl group.
【００２２】Ｒ1 、Ｒ2 で表されるアルケニル基として
は、総炭素数６〜５０のものが好ましく、無置換のもの
であってもよいが置換基を有するものであってもよく、
置換基を有する方が好ましい。このときの置換基として
は、フェニル基等のアリール基が好ましい。具体的に
は、トリフェニルビニル基、トリトリルビニル基、トリ
ビフェニルビニル基等が挙げられる。The alkenyl group represented by R 1 and R 2 preferably has 6 to 50 carbon atoms, and may be unsubstituted or may have a substituent.
It is preferable to have a substituent. The substituent at this time is preferably an aryl group such as a phenyl group. Specific examples include a triphenylvinyl group, a tolylvinyl group, and a tribiphenylvinyl group.
【００２３】Ｒ1 、Ｒ2 で表されるアルコキシ基として
は、アルキル基部分の炭素数が１〜６のものが好まし
く、具体的にはメトキシ基、エトキシ基等が挙げられ
る。アルコキシ基は、さらに置換されていてもよい。The alkoxy group represented by R 1 and R 2 preferably has 1 to 6 carbon atoms in the alkyl group, and specific examples include a methoxy group and an ethoxy group. The alkoxy group may be further substituted.
【００２４】Ｒ1 、Ｒ2 で表されるアリーロキシ基とし
ては、フェノキシ基等が挙げられる。Examples of the aryloxy group represented by R 1 and R 2 include a phenoxy group.
【００２５】Ｒ1 、Ｒ2 で表されるアミノ基は、無置換
でも置換基を有するものであってもよいが、置換基を有
することが好ましく、この場合の置換基としてはアルキ
ル基（メチル基、エチル基等）、アリール基（フェニル
基等）などが挙げられる。具体的にはジエチルアミノ
基、ジフェニルアミノ基、ジ（ｍ−トリル）アミノ基等
が挙げられる。The amino group represented by R 1 or R 2 may be unsubstituted or substituted, but preferably has a substituent. In this case, the substituent is preferably an alkyl group (methyl Group, an ethyl group, etc.) and an aryl group (a phenyl group, etc.). Specific examples include a diethylamino group, a diphenylamino group, and a di (m-tolyl) amino group.
【００２６】Ｒ1 、Ｒ2 で表される複素環基としては、
ビピリジル基、ピリミジル基、キノリル基、ピリジル
基、チエニル基、フリル基、オキサジアゾイル基等が挙
げられる。これらは、メチル基、フェニル基等の置換基
を有していてもよい。The heterocyclic groups represented by R 1 and R 2 include:
Examples include a bipyridyl group, a pyrimidyl group, a quinolyl group, a pyridyl group, a thienyl group, a furyl group, and an oxadiazoyl group. These may have a substituent such as a methyl group or a phenyl group.
【００２７】化５および化６において、ｒ１およびｒ２
は、各々、０または１〜５の整数を表し、特に、０〜２
であることが好ましい。ｒ１およびｒ２が、各々、１〜
５の整数、特に１または２であるとき、Ｒ1 およびＲ2
は、各々、アルキル基、アリール基、アルケニル基、ア
ルコキシ基、アリーロキシ基、アミノ基であることが好
ましい。In the chemical formulas 5 and 6, r1 and r2
Represents 0 or an integer of 1 to 5;
It is preferred that r1 and r2 are each 1 to
When an integer of 5, especially 1 or 2, R 1 and R 2
Is preferably an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, or an amino group, respectively.
【００２８】化５および化６において、Ｒ1 とＲ2 とは
同一でも異なるものであってもよく、Ｒ1 とＲ2 とが各
々複数存在するとき、Ｒ1 同士、Ｒ2 同士は各々同一で
も異なるものであってもよく、Ｒ1 同士あるいはＲ2 同
士は結合してベンゼン環等の環を形成してもよく、環を
形成する場合も好ましい。In the chemical formulas (5) and (6), R 1 and R 2 may be the same or different. When a plurality of R 1 and R 2 are present, R 1 and R 2 are the same. However, R 1 and R 2 may be bonded to each other to form a ring such as a benzene ring, and it is also preferable to form a ring.
【００２９】化５および化６で示されるフェニルアント
ラセン誘導体のなかでも、化７および化８で示されるも
のが好ましい。ここで、化７における Ｒ51 およびＲ52
は、化５におけるＲ1 およびＲ2 と、また化８におけ
るＲ53 およびＲ54 は、化６におけるＲ3 およびＲ
4と、それぞれ同義であり、好ましいものも同様であ
る。Among the phenylanthracene derivatives represented by Chemical Formulas 5 and 6, those represented by Chemical Formulas 7 and 8 are preferable. Here, R 51 and R 52 in Chemical formula 7
Is the same as R 1 and R 2 in Chemical Formula 5, and R 53 and R 54 in Chemical Formula 8 are R 3 and R in Chemical Formula 6.
And 4 are synonymous with each other, and preferred ones are also the same.
【００３０】化５と化６の化合物、または化７と化８の
化合物の混合比は、重量比でほぼ１：１の場合が効率、
寿命ともに最大となるが、混合比が重量比で４：１〜
１：４程度の場合でも効率の減少は約１割程度であり、
さらに９５：５の場合でも１５％程度であり、従来のド
ーピング法とは異なり非常に広い製造マージンを有して
いる。このため、化５と化６の化合物、または化７と化
８の化合物の混合比は、９５：５〜２０：８０wt％が好
ましく、特に８０：２０〜５０：５０wt％が好ましい。The mixing ratio of the compounds of the formulas (5) and (6) or the compounds of the formulas (7) and (8) is approximately 1: 1 in terms of weight ratio,
The life is maximized, but the mixing ratio is 4: 1 to 1 by weight.
Even when the ratio is about 1: 4, the efficiency decreases by about 10%.
Furthermore, even in the case of 95: 5, it is about 15%, which has a very wide manufacturing margin unlike the conventional doping method. For this reason, the mixing ratio of the compounds of formulas (5) and (6) or the compounds of formulas (7) and (8) is preferably from 95: 5 to 20:80 wt%, particularly preferably from 80:20 to 50:50 wt%.
【００３１】化５および化６で示される化合物を以下に
例示するが、本発明はこれらに限定されるものではな
い。なお、化９、化１２では一般式を示し、化１０、化
１１、化１３、化１４で、それぞれ対応する具体例をＲ
11 〜Ｒ15 、Ｒ21 〜Ｒ25 、あるいはＲ31 〜Ｒ35 、Ｒ
41 〜Ｒ45 の組み合わせで示している。The compounds represented by the formulas (5) and (6) are exemplified below, but the present invention is not limited thereto. In addition, chemical formulas 9 and 12 show general formulas, and chemical formulas 10, 11 and 13 correspond to specific examples of R, respectively.
11 to R 15 , R 21 to R 25 , or R 31 to R 35 , R
Shows a combination of 41 to R 45.
【００３２】[0032]
【化９】 Embedded image
【００３３】[0033]
【化１０】 Embedded image
【００３４】[0034]
【化１１】 Embedded image
【００３５】[0035]
【化１２】 Embedded image
【００３６】[0036]
【化１３】 Embedded image
【００３７】[0037]
【化１４】 Embedded image
【００３８】本発明の混合層に使用されるフェニルアン
トラセン誘導体は、（１）ハロゲン化ジフェニルアント
ラセン化合物を、Ｎｉ（ｃｏｄ）2 〔ｃｏｄ：１，５−
シクロオクタジエン〕でカップリング、もしくはジハロ
ゲン化アリールをグリニャール化しＮｉＣｌ2 （ｄｐｐ
ｅ）［ｄｐｐｅ：ジフェニルフォスフィノエタン］、Ｎ
ｉＣｌ2 （ｄｐｐｐ）〔ｄｐｐｐ：ジフェニルフォスフ
ィノプロパン〕、などのＮｉ錯体などを用いてクロスカ
ップリングする方法、（２）アントラキノン、ベンゾキ
ノン、フェニルアンスロンもしくはビアントロンとグリ
ニャール化したアリールもしくはリチオ化したアリール
との反応および還元によりクロスカップリングする方
法、等により得られる。The phenylanthracene derivative used in the mixed layer of the present invention comprises (1) a halogenated diphenylanthracene compound formed by converting Ni (cod) 2 [cod: 1,5-
Cyclooctadiene] or Grignard of an aryl dihalide is converted to NiCl 2 (dpp
e) [dppe: diphenylphosphinoethane], N
a method of cross-coupling using a Ni complex such as iCl 2 (dppp) [dppp: diphenylphosphinopropane], (2) aryl or lithiated aryl Grignarded with anthraquinone, benzoquinone, phenylanthrone or Bianthrone And a method of cross-coupling by reduction and the like.
【００３９】このようにして得られた化合物は、元素分
析、質量分析、赤外吸収スペクトル、 1Ｈまたは13Ｃ核
磁気共鳴吸収（ＮＭＲ）スペクトルなどによって同定す
ることができる。The compound thus obtained can be identified by elemental analysis, mass spectrometry, infrared absorption spectrum, 1 H or 13 C nuclear magnetic resonance absorption (NMR) spectrum, and the like.
【００４０】また、このフェニルアントラセン誘導体
は、４００〜２０００程度、さらには４００〜１０００
程度の分子量をもち、２００〜５００℃の高融点を有
し、８０〜２５０℃、さらには１００〜２５０℃、より
さらには１３０〜２５０℃、特に１４０〜２５０℃のガ
ラス転移温度（Ｔｇ）を示す。従って、通常の真空蒸着
等により透明で室温以上でも安定なアモルファス状態の
平滑で良好な膜を形成し、しかもその良好な膜の状態が
長期間に渡って維持される。The phenylanthracene derivative is used in an amount of about 400 to 2,000,
It has a high melting point of 200-500 ° C. and a glass transition temperature (Tg) of 80-250 ° C., more preferably 100-250 ° C., even more 130-250 ° C., especially 140-250 ° C. Show. Accordingly, a smooth and good film in an amorphous state, which is transparent and stable even at room temperature or higher, is formed by ordinary vacuum evaporation or the like, and the good film state is maintained for a long period of time.
【００４１】本発明の有機ＥＬ素子（以下、「ＥＬ素
子」ともいう。）は、少なくとも１層の有機化合物混合
層を有し、この混合層が２種以上のフェニルアントラセ
ン誘導体を含有する有機層で構成されている。本発明の
有機ＥＬ素子の構成例を図１に示す。同図に示される有
機ＥＬ素子は、基板１上に、陽極２、ホール注入輸送層
３、発光層４、電子注入輸送層５、陰極６を順次有す
る。The organic EL device of the present invention (hereinafter also referred to as “EL device”) has at least one organic compound mixed layer, and this mixed layer contains two or more kinds of phenylanthracene derivatives. It is composed of FIG. 1 shows a configuration example of the organic EL element of the present invention. The organic EL device shown in FIG. 1 has an anode 2, a hole injection / transport layer 3, a light emitting layer 4, an electron injection / transport layer 5, and a cathode 6 in that order on a substrate 1.
【００４２】発光層は、ホールおよび電子の注入機能、
それらの輸送機能、ホールと電子の再結合により励起子
を生成させる機能を有する。ホール注入輸送層は、陽極
からのホールの注入を容易にする機能、ホールを輸送す
る機能および電子の輸送を妨げる機能を有し、電子注入
輸送層は、陰極からの電子の注入を容易にする機能、電
子を輸送する機能およびホールの輸送を妨げる機能を有
するものであり、これらの層は、発光層へ注入されるホ
ールや電子を増大・閉じ込めさせ、再結合領域を最適化
させ、発光効率を改善する。電子注入輸送層およびホー
ル注入輸送層は、発光層に用いる化合物の電子注入、電
子輸送、ホール注入、ホール輸送の各機能の高さを考慮
し、必要に応じて設けられる。例えば、発光層に用いる
化合物のホール注入輸送機能または電子注入輸送機能が
高い場合には、ホール注入輸送層または電子注入輸送層
を設けずに、発光層がホール注入輸送層または電子注入
輸送層を兼ねる構成とすることができる。また、場合に
よってはホール注入輸送層および電子注入輸送層のいず
れも設けなくてよい。また、ホール注入輸送層および電
子注入輸送層は、それぞれにおいて、注入機能をもつ層
と輸送機能をもつ層とを別個に設けてもよい。The light emitting layer has a hole and electron injection function,
They have a transport function and a function of generating excitons by recombination of holes and electrons. The hole injection transport layer has a function of facilitating the injection of holes from the anode, a function of transporting holes, and a function of preventing the transport of electrons, and the electron injection transport layer facilitates the injection of electrons from the cathode. These layers have the function of transporting electrons and the function of preventing the transport of holes. These layers increase and confine holes and electrons injected into the light emitting layer, optimize the recombination region, and improve the luminous efficiency. To improve. The electron injecting / transporting layer and the hole injecting / transporting layer are provided as necessary in consideration of the electron injecting, electron transporting, hole injecting, and hole transporting functions of the compound used in the light emitting layer. For example, in the case where the compound used for the light emitting layer has a high hole injection / transport function or electron injection / transport function, the light emitting layer is provided with the hole injection / transport layer or the electron injection / transport layer without providing the hole injection / transport layer or the electron injection / transport layer. A configuration that can also serve as a combination can be adopted. In some cases, neither the hole injection transport layer nor the electron injection transport layer may be provided. Further, each of the hole injection / transport layer and the electron injection / transport layer may be separately provided with a layer having an injection function and a layer having a transport function.
【００４３】本発明の混合層は、比較的ニュートラルな
ので発光層に用いることが好ましいが、ホール注入輸送
層や電子注入輸送層にも適用可能である。また、本発明
の混合層により、単層でホール注入輸送層、電子注入輸
送層、発光層を兼ねることも可能である。Since the mixed layer of the present invention is relatively neutral, it is preferably used for the light emitting layer. However, the mixed layer is also applicable to the hole injection transport layer and the electron injection transport layer. Further, the mixed layer of the present invention allows a single layer to also serve as a hole injection / transport layer, an electron injection / transport layer, and a light emitting layer.
【００４４】また、組み合わせる発光層や電子注入輸送
層やホール注入輸送層のキャリア移動度やキャリア密度
（イオン化ポテンシャル・電子親和力により決まる）を
考慮しながら、膜厚をコントロールすることで、再結合
領域・発光領域を自由に設計することが可能であり、発
光色の設計や、両電極の干渉効果による発光輝度・発光
スペクトルの制御や、発光の空間分布の制御を可能にで
きる。Further, by controlling the film thickness in consideration of the carrier mobility and carrier density (determined by ionization potential and electron affinity) of the combined light emitting layer, electron injection transport layer and hole injection transport layer, the recombination region can be controlled. It is possible to freely design a light emitting region, and it is possible to design a light emitting color, control light emission luminance and light emission spectrum by an interference effect between both electrodes, and control a spatial distribution of light emission.
【００４５】本発明の混合層を発光層に用いる場合につ
いて説明する。発光層には本発明の化合物のほか、他の
蛍光性物質を用いてもよく、他の蛍光性物質としては、
例えば、特開昭６３−２６４６９２号公報に開示されて
いるような化合物、例えば、キナクリドン、ルブレン、
スチリル系色素等の化合物から選択される少なくとも１
種が挙げられる。このような蛍光性物質の含有量は、本
発明の化合物の１０モル％以下とすることが好ましい。
このような化合物を適宜選択して添加することにより、
発光光を長波長側にシフトすることができる。The case where the mixed layer of the present invention is used for a light emitting layer will be described. In addition to the compound of the present invention, other fluorescent substances may be used for the light-emitting layer.
For example, compounds as disclosed in JP-A-63-264892, such as quinacridone, rubrene,
At least one selected from compounds such as styryl dyes
Seeds. It is preferable that the content of such a fluorescent substance is 10 mol% or less of the compound of the present invention.
By appropriately selecting and adding such a compound,
The emitted light can be shifted to a longer wavelength side.
【００４６】また、発光層には、一重項酸素クエンチャ
ーが含有されていてもよい。このようなクエンチャーと
しては、ニッケル錯体や、ルブレン、ジフェニルイソベ
ンゾフラン、三級アミン等が挙げられる。このようなク
エンチャーの含有量は、本発明の化合物の１０モル％以
下とすることが好ましい。Further, the light emitting layer may contain a singlet oxygen quencher. Examples of such a quencher include a nickel complex, rubrene, diphenylisobenzofuran, and a tertiary amine. The content of such a quencher is preferably 10 mol% or less of the compound of the present invention.
【００４７】本発明の混合層を発光層に用いる場合、ホ
ール注入輸送層および電子注入輸送層には、通常の有機
ＥＬ素子に用いられている各種有機化合物、例えば、特
開昭６３−２９５６９５号公報、特開平２−１９１６９
４号公報、特開平３−７９２号公報等に記載されている
各種有機化合物を用いることができる。例えば、ホール
注入輸送層には、芳香族三級アミン、ヒドラゾン誘導
体、カルバゾール誘導体、トリアゾール誘導体、イミダ
ゾール誘導体等を用いることができ、また、電子注入輸
送層には、アルミキノリノールなどの有機金属錯体誘導
体、オキサジアゾール誘導体、ピリジン誘導体、ピリミ
ジン誘導体、キノリン誘導体、キノキサリン誘導体、ジ
フェニルキノン誘導体、ペリレン誘導体、フルオレン誘
導体等を用いることができる。When the mixed layer according to the present invention is used for the light emitting layer, the hole injection transport layer and the electron injection transport layer may include various organic compounds used in ordinary organic EL devices, for example, JP-A-63-295695. Gazette, JP-A-2-19169
Various organic compounds described in JP-A No. 4 and JP-A-3-792 can be used. For example, an aromatic tertiary amine, a hydrazone derivative, a carbazole derivative, a triazole derivative, an imidazole derivative, or the like can be used for the hole injection / transport layer, and an organic metal complex derivative such as aluminum quinolinol can be used for the electron injection / transport layer. Oxadiazole derivatives, pyridine derivatives, pyrimidine derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, perylene derivatives, fluorene derivatives, and the like.
【００４８】ホール注入輸送層をホール注入層とホール
輸送層とに分けて設層する場合は、ホール注入輸送層用
の化合物のなかから好ましい組合せを選択して用いるこ
とができる。このとき、陽極（ＩＴＯ等）側からイオン
化ポテンシャルの小さい化合物の層の順に積層すること
が好ましい。また陽極表面には薄膜性の良好な化合物を
用いることが好ましい。このような積層順については、
ホール注入輸送層を２層以上設けるときも同様である。
このような積層順とすることによって、駆動電圧が低下
し、電流リークの発生やダークスポットの発生・成長を
防ぐことができる。また、素子化する場合、蒸着を用い
ているので１〜１０nm程度の薄い膜も、均一かつピンホ
ールフリーとすることができるため、ホール注入層にイ
オン化ポテンシャルが小さく、可視部に吸収をもつよう
な化合物を用いても、発光色の色調変化や再吸収による
効率の低下を防ぐことができる。When the hole injecting and transporting layer is provided separately for the hole injecting and transporting layers, a preferred combination can be selected from the compounds for the hole injecting and transporting layer. At this time, it is preferable to stack the layers of the compound having the smaller ionization potential in order from the anode (ITO or the like) side. It is preferable to use a compound having good thin film properties on the anode surface. For such a stacking order,
The same applies when two or more hole injection / transport layers are provided.
With such a stacking order, the driving voltage is reduced, and the occurrence of current leakage and the occurrence and growth of dark spots can be prevented. In the case of forming an element, a thin film of about 1 to 10 nm can be made uniform and pinhole-free because of the use of vapor deposition, so that the hole injection layer has a small ionization potential and has absorption in the visible part. Even when such a compound is used, it is possible to prevent a change in the color tone of the emission color or a decrease in efficiency due to reabsorption.
【００４９】電子注入輸送層を電子注入層と電子輸送層
とに分けて設層する場合は、電子注入輸送層用の化合物
のなかから好ましい組合せを選択して用いることができ
る。このとき、陰極側から電子親和力の値の大きい化合
物の層の順に積層することが好ましい。このような積層
順については電子注入輸送層を２層以上設けるときも同
様である。When the electron injecting and transporting layer is provided separately for the electron injecting layer and the electron transporting layer, a preferable combination can be selected from the compounds for the electron injecting and transporting layer. At this time, it is preferable to stack the layers of the compound having the largest electron affinity value from the cathode side. This stacking order is the same when two or more electron injection / transport layers are provided.
【００５０】発光層の厚さ、ホール注入輸送層の厚さお
よび電子注入輸送層の厚さは特に限定されず、形成方法
によっても異なるが、通常、５〜１０００nm程度、特に
８〜２００nmとすることが好ましい。The thickness of the light emitting layer, the thickness of the hole injecting and transporting layer, and the thickness of the electron injecting and transporting layer are not particularly limited, and vary depending on the forming method, but are usually about 5 to 1000 nm, especially 8 to 200 nm. Is preferred.
【００５１】ホール注入輸送層の厚さおよび電子注入輸
送層の厚さは、再結合・発光領域の設計によるが、発光
層の厚さと同程度もしくは１／１０〜１０倍程度とすれ
ばよい。電子もしくはホールの、各々の注入層と輸送層
を分ける場合は、注入層は１nm以上、輸送層は２０nm以
上とするのが好ましい。このときの注入層、輸送層の厚
さの上限は、通常、注入層で１００nm程度、輸送層で１
０００nm程度である。The thickness of the hole injecting and transporting layer and the thickness of the electron injecting and transporting layer depend on the design of the recombination / light emitting region, but may be about the same as the thickness of the light emitting layer or about 1/10 to 10 times. When the injection layer and the transport layer for electrons or holes are separated from each other, the thickness of the injection layer is preferably 1 nm or more, and the thickness of the transport layer is preferably 20 nm or more. At this time, the upper limit of the thickness of the injection layer and the transport layer is usually about 100 nm in the injection layer and 1 in the transport layer.
It is about 000 nm.
【００５２】陰極には、仕事関数の小さい材料、例え
ば、Ｌｉ、Ｎａ、Ｍｇ、Ａｌ、Ａｇ、Ｉｎあるいはこれ
らの１種以上を含む合金、あるいはこれらの酸化物、ハ
ロゲン化物を用いることが好ましい。また、陰極は結晶
粒が細かいことが好ましく、特に、アモルファス状態で
あることが好ましい。陰極の厚さは１０〜１０００nm程
度とすることが好ましい。For the cathode, it is preferable to use a material having a small work function, for example, Li, Na, Mg, Al, Ag, In or an alloy containing at least one of these, or an oxide or halide thereof. The cathode preferably has fine crystal grains, and particularly preferably has an amorphous state. The thickness of the cathode is preferably about 10 to 1000 nm.
【００５３】ＥＬ素子を面発光させるためには、少なく
とも一方の電極が透明ないし半透明である必要があり、
上記したように陰極の材料には制限があるので、好まし
くは発光光の透過率が８０％以上となるように陽極の材
料および厚さを決定することが好ましい。具体的には、
例えば、ＩＴＯ、ＳｎＯ2 、Ｎｉ、Ａｕ、Ｐｔ、Ｐｄ、
ドーパントをドープしたポリピロールなどを陽極に用い
ることが好ましい。また、陽極の厚さは１０〜５００nm
程度とすることが好ましい。また、素子の信頼性を向上
するために駆動電圧が低いことが必要であるが、好まし
いものとして１０〜３０Ω／□程度ないし１０Ω／□以
下（通常５〜１０Ω／□）のＩＴＯが挙げられる。In order for the EL element to emit light from the surface, at least one of the electrodes must be transparent or translucent.
Since the material of the cathode is limited as described above, it is preferable to determine the material and the thickness of the anode such that the transmittance of emitted light is preferably 80% or more. In particular,
For example, ITO, SnO 2 , Ni, Au, Pt, Pd,
It is preferable to use polypyrrole doped with a dopant for the anode. The thickness of the anode is 10 to 500 nm.
It is preferable to set the degree. Further, it is necessary that the driving voltage is low in order to improve the reliability of the element. As a preferable one, ITO of about 10 to 30 Ω / □ to 10 Ω / □ or less (usually 5 to 10 Ω / □) is exemplified.
【００５４】基板材料に特に制限はないが、図示例では
基板側から発光光を取り出すため、ガラスや樹脂等の透
明ないし半透明材料を用いる。また、基板に色フィルタ
ー膜や誘電体反射膜を用いて発光色をコントロールして
もよい。There is no particular limitation on the material of the substrate, but in the illustrated example, a transparent or translucent material such as glass or resin is used to extract emitted light from the substrate side. The emission color may be controlled by using a color filter film or a dielectric reflection film on the substrate.
【００５５】なお、基板に不透明な材料を用いる場合、
基板と反対側から発光を取り出す場合等には、図１に示
される積層順序を逆にしてもよい。When an opaque material is used for the substrate,
When light emission is taken out from the side opposite to the substrate, the stacking order shown in FIG. 1 may be reversed.
【００５６】次に、本発明の有機ＥＬ素子の製造方法を
説明する。陰極および陽極は、蒸着法やスパッタ法等の
気相成長法により形成することが好ましい。Next, a method for manufacturing the organic EL device of the present invention will be described. The cathode and anode are preferably formed by a vapor deposition method such as an evaporation method or a sputtering method.
【００５７】ホール注入輸送層、発光層および電子注入
輸送層の形成には、均質な薄膜が形成できることから真
空蒸着法を用いることが好ましい。真空蒸着法を用いた
場合、アモルファス状態または結晶粒径が０．２μm 以
下（通常０．０１μm 以上）の均質な薄膜が得られる。
結晶粒径が０．２μm を超えていると、不均一な発光と
なり、素子の駆動電圧を高くしなければならなくなり、
電荷の注入効率も著しく低下する。For forming the hole injection transport layer, the light emitting layer and the electron injection transport layer, it is preferable to use a vacuum deposition method since a uniform thin film can be formed. When a vacuum deposition method is used, a homogeneous thin film having an amorphous state or a crystal grain size of 0.2 μm or less (usually 0.01 μm or more) can be obtained.
If the crystal grain size exceeds 0.2 μm, the light emission becomes non-uniform, and the driving voltage of the device must be increased.
The charge injection efficiency is also significantly reduced.
【００５８】真空蒸着の条件は特に限定されないが、
１．３×１０-3Pa(１０-5Torr)以下の真空度とし、蒸着
速度は０．１〜１nm／sec 程度とすることが好ましい。
また、真空中で連続して各層を形成することが好まし
い。真空中で連続して形成すれば、各層の界面に不純物
が吸着することを防げるため、高特性が得られる。ま
た、素子の駆動電圧を低くすることができる。The conditions for vacuum deposition are not particularly limited.
The degree of vacuum is preferably 1.3 × 10 −3 Pa (10 −5 Torr) or less, and the deposition rate is preferably about 0.1 to 1 nm / sec.
Further, it is preferable to form each layer continuously in a vacuum. If they are formed continuously in a vacuum, impurities can be prevented from adsorbing at the interface between the layers, so that high characteristics can be obtained. Further, the driving voltage of the element can be reduced.
【００５９】これら各層の形成に真空蒸着法を用いる場
合において、１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水晶振動子
膜厚計でモニターしながら共蒸着することが好ましい。In the case where a plurality of compounds are contained in one layer when a vacuum evaporation method is used to form each of these layers, each boat containing the compounds is individually temperature-controlled and monitored with a quartz crystal film thickness meter. Co-evaporation is preferred.
【００６０】本発明のＥＬ素子は、通常、直流駆動型の
ＥＬ素子として用いられるが、交流駆動またはパルス駆
動することもできる。印加電圧は、通常、２〜２０V 程
度とされる。The EL element of the present invention is usually used as a DC-driven EL element, but can be driven by AC or pulse. The applied voltage is usually about 2 to 20V.
【００６１】[0061]
【実施例】以下、本発明の具体的実施例を合成例、比較
例とともに示し、本発明をさらに詳細に説明する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention, together with synthesis examples and comparative examples.
【００６２】＜合成例１＞ 例示化合物Ｉ-２８（10,10’-ビス（2-ビフェニルイ
ル）-9,9’-ビアンスリル）の合成 ２−ブロモビフェニル７．８g、ジエチルエーテル５０m
lとトルエン５０mlを混合し、これに１．６Mブチルリチ
ウムのヘキサン溶液２０．４mlをゆっくり滴下しながら
１時間室温で攪拌し、２−リチオビフェニルを調整し
た。次に、トルエン１５０mlとビアンスロン４gの混合
物にこのリチオビフェニルをゆっくり滴下し、室温で一
昼夜攪拌した。次いで、これに蒸留水１００mlを加えさ
らに１時間攪拌した後、この溶液を濾過し、廬物をトル
エン、メタノールで洗浄した。得られた物をテトラヒド
ロフランとトルエンから再結晶した後、カラム精製し、
４．３g の白色固体としてジオール体を得た。<Synthesis Example 1> Synthesis of Exemplified Compound I-28 (10,10'-bis (2-biphenylyl) -9,9'-bianthryl) 7.8 g of 2-bromobiphenyl, 50 m of diethyl ether
The mixture was stirred at room temperature for 1 hour while slowly adding dropwise 20.4 ml of a 1.6 M butyllithium hexane solution to prepare 2-lithiobiphenyl. Next, this lithiobiphenyl was slowly dropped into a mixture of 150 ml of toluene and 4 g of Bianthrone, followed by stirring at room temperature for 24 hours. Then, 100 ml of distilled water was added thereto, and the mixture was further stirred for 1 hour. Then, the solution was filtered, and the residue was washed with toluene and methanol. After recrystallizing the obtained product from tetrahydrofuran and toluene, column purification was performed,
The diol was obtained as 4.3 g of a white solid.
【００６３】このジオール体４g とテトラヒドロフラン
４００mlをフラスコに入れ塩化すず２５g と塩酸２５ml
を混合した溶液をゆっくり滴下した。このフラスコを７
０度のオイルバスで２時間加熱した後冷却し、２００ml
のトルエンを加え、蒸留水及び炭酸水素ナトリウムで洗
浄した。硫酸マグネシウムで乾燥した後、カラム精製と
再沈を繰り返し、３．７g の淡黄白色固体を得た。この
淡黄白色固体３．０gを昇華精製し２．８g の黄白色固
体を得た。この目的物（10,10’-ビス（2-ビフェニルイ
ル）-9,9’-ビアンスリル）の構造を下記に示す。4 g of this diol and 400 ml of tetrahydrofuran are placed in a flask, and 25 g of tin chloride and 25 ml of hydrochloric acid are placed.
Was slowly added dropwise. This flask is
After heating in a 0 degree oil bath for 2 hours, cool, 200ml
And washed with distilled water and sodium hydrogen carbonate. After drying over magnesium sulfate, column purification and reprecipitation were repeated to obtain 3.7 g of a pale yellow-white solid. Sublimation purification of 3.0 g of this pale yellow-white solid gave 2.8 g of a yellow-white solid. The structure of this target product (10,10′-bis (2-biphenylyl) -9,9′-bianthryl) is shown below.
【００６４】[0064]
【化１５】 Embedded image
【００６５】この黄白色個体の質量分析およびＮＭＲス
ペクトル、赤外吸収スペクトルの測定を行ったところ、
目的物と矛盾しないことを確認した。また、ガラス転移
温度を測定したところ、１４４度であった。When the mass spectrometry, NMR spectrum and infrared absorption spectrum of this yellow-white solid were measured,
It was confirmed that it was not inconsistent with the object. The glass transition temperature was measured to be 144 degrees.
【００６６】＜合成例２＞ 例示化合物II-２１（９,９’,10,10’-テトラキス（-2-
ビフェニルイル）-2,2’-ビアンスリル）の合成 ２−ブロモビフェニル１１．４g、ジエチルエーテル５
０mlとトルエン５０m１を混合し、これに１．６Mブチル
リチウムのヘキサン溶液３０をゆっくり滴下しながら１
時間室温で攪拌し、２−リチオビフェニルを調整した。
次に、トルエン１５０mlと２−クロロアントラキノン
５．５gの混合物にこのリチオビフェニルをゆっくり滴
下し、室温で一昼夜攪拌した。次いで、これに蒸留水１
００mlを加えさらに１時間攪拌した後、この溶液を濾過
し、廬物をメタノールで洗浄した。得られた物を再結晶
した後、カラム精製し、９．８g の白色固体としてジオ
ール体を得た。<Synthesis Example 2> Illustrative compound II-21 (9,9 ', 10,10'-tetrakis (-2-
Synthesis of biphenylyl) -2,2'-bianthryl) 11.4 g of 2-bromobiphenyl, diethyl ether 5
0 ml and toluene (50 ml) were mixed, and 1.6 M butyl lithium hexane solution 30 was slowly added dropwise to the mixture.
The mixture was stirred at room temperature for 2 hours to prepare 2-lithiobiphenyl.
Next, this lithiobiphenyl was slowly dropped into a mixture of 150 ml of toluene and 5.5 g of 2-chloroanthraquinone, and the mixture was stirred at room temperature for 24 hours. Then, add distilled water 1
After adding 00 ml and stirring for further 1 hour, the solution was filtered and the residue was washed with methanol. The obtained product was recrystallized and purified by column to obtain 9.8 g of a diol as a white solid.
【００６７】このジオール体９．６g とテトラヒドロフ
ラン４００mlを混合し、これに塩化すず２５gと塩酸２
５mlの混合液をゆっくり滴下した。さらに、これを７０
度のオイルバスで２時間加熱した後冷却し、２００mlの
トルエンを加え、蒸留水及び炭酸水素ナトリウムで洗浄
した。硫酸マグネシウムで乾燥した後、カラム精製と再
沈を繰り返し、純白色の２−クロロ−９,１０−ジフェ
ニルアントラセン７．１g を得た。9.6 g of this diol was mixed with 400 ml of tetrahydrofuran, and 25 g of tin chloride and 2 ml of hydrochloric acid were added.
5 ml of the mixture was slowly added dropwise. Furthermore, this is 70
After heating in an oil bath for 2 hours, the mixture was cooled, 200 ml of toluene was added, and the mixture was washed with distilled water and sodium hydrogen carbonate. After drying over magnesium sulfate, column purification and reprecipitation were repeated to obtain 7.1 g of pure white 2-chloro-9,10-diphenylanthracene.
【００６８】次に、２−クロロ−９,１０−ジフェニル
アントラセン４．５g、Ni(cod)2１．８g、DMF１００m
l、１,５−シクロオクタジエン３ml、２,２’−ビピリ
ジン１gを混合し、６０度で２０時間反応した後、これ
をメタノール２００mlに加え、さらに２時間攪拌した。
この溶液を濾過し、廬物をメタノール、ヘキサン、アセ
トンで洗浄した後、再結晶およびカラム精製を行い、３
g の白色固体を得た。これを昇華精製し、２．８gの黄
白色個体を得た。得られた目的物の構造を下記に示す。Next, 4.5 g of 2-chloro-9,10-diphenylanthracene, 21.8 g of Ni (cod) and 100 m of DMF
l, 1,5-Cyclooctadiene (3 ml), 2,2′-bipyridine (1 g) were mixed and reacted at 60 ° C. for 20 hours, and the mixture was added to methanol (200 ml) and further stirred for 2 hours.
The solution was filtered, and the residue was washed with methanol, hexane, and acetone.
g of a white solid were obtained. This was sublimated and purified to obtain 2.8 g of a yellow-white solid. The structure of the obtained target product is shown below.
【００６９】[0069]
【化１６】 Embedded image
【００７０】この黄白色個体の質量分析およびＮＭＲス
ペクトル、赤外吸収スペクトルの測定を行ったところ、
目的物と矛盾しないことを確認した。また、ガラス転移
温度を測定したところ、１６６度であった。When the mass spectrometry, NMR spectrum and infrared absorption spectrum of this yellow-white solid were measured,
It was confirmed that it was not inconsistent with the object. The glass transition temperature was measured to be 166 degrees.
【００７１】なお、ガラス上に蒸着して放置したところ
半年以上アモルファスの安定な膜を維持した。When the film was deposited on glass and allowed to stand, an amorphous stable film was maintained for more than half a year.
【００７２】＜実施例１＞厚さ１００nmのＩＴＯ透明電
極（陽極）を有するガラス基板を、中性洗剤、アセト
ン、エタノールを用いて超音波洗浄し、煮沸エタノール
中から引き上げて乾燥した。透明電極表面をUV/O3 洗浄
した後、真空蒸着装置の基板ホルダーに固定して、１×
１０-4 Pa以下まで減圧した。Example 1 A glass substrate having an ITO transparent electrode (anode) having a thickness of 100 nm was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol, pulled up from boiling ethanol, and dried. After cleaning the transparent electrode surface with UV / O 3 , fix it to the substrate holder of
The pressure was reduced to 10 −4 Pa or less.
【００７３】次いで、減圧状態を保ったまま、Ｎ，Ｎ’
−ジフェニル−Ｎ，Ｎ’−ビス[N−(４-メチルフェニ
ル）− N−フェニル-（４-アミノフェニル）]−１，
１’−ビフェニル−４，４’−ジアミンを蒸着速度０．
１nm/secで８０nmの厚さに蒸着し、ホール注入層とし
た。Next, N, N 'is maintained while maintaining the reduced pressure.
-Diphenyl-N, N'-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]-1,
1′-biphenyl-4,4′-diamine was deposited at a deposition rate of 0.1%.
Evaporation was performed at 1 nm / sec to a thickness of 80 nm to form a hole injection layer.
【００７４】次いで、 Ｎ，Ｎ’−ジフェニル− Ｎ，
Ｎ’−ジナフチル−ベンジジンを蒸着速度０．１nm/sec
で１５nmの厚さに蒸着し、ホール輸送層とした。Next, N, N'-diphenyl-N,
N'-dinaphthyl-benzidine was deposited at a deposition rate of 0.1 nm / sec.
Was deposited to a thickness of 15 nm to form a hole transport layer.
【００７５】さらに、減圧状態を保ったまま、例示化合
物（Ｉ−２８）と例示化合物（II-２１）を重量比９
５：５で全体の蒸着速度０．１５〜０．２０nm/secで４
０nmの厚さに蒸着し、発光層とした。Further, while maintaining the reduced pressure, the exemplified compound (I-28) and the exemplified compound (II-21) were added at a weight ratio of 9
5: 5 at an overall deposition rate of 0.15 to 0.20 nm / sec.
Evaporation was performed to a thickness of 0 nm to form a light emitting layer.
【００７６】さらに、減圧状態を保ったまま、Ｌｉ2Ｏ
を蒸着速度０．１nm/secで０．３nmの厚さに蒸着して電
子注入陰極とし、保護電極としてＡｌを１５０nm蒸着
し、有機ＥＬ素子を得た。Further, while maintaining the reduced pressure, Li 2 O
Was deposited to a thickness of 0.3 nm at a deposition rate of 0.1 nm / sec to form an electron injection cathode, and 150 nm of Al was deposited as a protective electrode to obtain an organic EL device.
【００７７】この有機ＥＬ素子に直流電圧を印加して電
流を流したところ、６．２V 、１０mA/cm2 で５６８cd/
m2 の発光（発光極大波長λmax ＝４６０nm、色度座標
（x,y）=（０．１５，０．２０）が確認された。[0077] When a current flows by applying a DC voltage to the organic EL element, 6.2 V, at 10mA / cm 2 568cd /
Light emission of m 2 (maximum emission wavelength λmax = 460 nm, chromaticity coordinates (x, y) = (0.15, 0.20)) was confirmed.
【００７８】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度２８００cd
/m2 で、輝度半減時間は１３０時間の寿命特性を示し
た。When a constant current of 50 mA / cm 2 was passed through the device to emit light continuously, the initial luminance was 2800 cd.
At / m 2 , the luminance half life was 130 hours.
【００７９】＜実施例２＞実施例１と同様に、ＩＴＯ付
きガラス基板の洗浄、ホール注入層、輸送層の蒸着成膜
を行った後、減圧を保ったまま、例示化合物Ｉ−２８と
例示化合物II-２１を重量比８０：２０で全体の蒸着速
度０．１５〜０．２０nm/secで４０nmの厚さに蒸着し、
発光層とした。さらに、実施例１と同様に電子輸送層、
電子注入電極、保護電極の成膜を行って、有機ＥＬ素子
を得た。Example 2 In the same manner as in Example 1, after cleaning the glass substrate with ITO and depositing the hole injection layer and the transport layer by vapor deposition, Exemplified Compound I-28 was illustrated while maintaining the reduced pressure. Compound II-21 is deposited to a thickness of 40 nm at a weight ratio of 80:20 at an overall deposition rate of 0.15 to 0.20 nm / sec,
It was a light emitting layer. Further, an electron transport layer as in Example 1,
An electron injecting electrode and a protective electrode were formed to obtain an organic EL device.
【００８０】このようにして得られた有機ＥＬ素子に対
して、実施例１と同様の特性評価を行ったところ、６．
０V 、１０mA/cm2 で６２６cd/m2 の発光（発光極大波
長λmax ＝４６５nm、色度座標（x,y）=（０．１５，
０．２１）が確認された。The obtained organic EL device was subjected to the same characteristic evaluation as in Example 1.
0V, 10mA / cm 2 emission of 626cd / m 2 by (emission maximum wavelength .lambda.max = 465 nm, the chromaticity coordinates (x, y) = (0.15 ,
0.21) was confirmed.
【００８１】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度３０１０cd
/m2 で、輝度半減時間は２３０時間の寿命特性を示し
た。When a constant current of 50 mA / cm 2 was passed through the device to continuously emit light, the initial luminance was 3010 cd
/ m 2 , the luminance half life was 230 hours.
【００８２】＜実施例３＞実施例１と同様に、ＩＴＯ付
きガラス基板の洗浄、ホール注入層、輸送層の蒸着成膜
を行った後、減圧を保ったまま、例示化合物Ｉ−２８と
例示化合物II-２１を重量比５０：５０で全体の蒸着速
度０．１５〜０．２０nm/secで４０nmの厚さに蒸着し、
発光層とした。さらに、実施例１と同様に電子輸送層、
電子注入電極、保護電極の成膜を行って、有機ＥＬ素子
を得た。Example 3 In the same manner as in Example 1, after cleaning the glass substrate with ITO, depositing the hole injection layer and the transport layer by vapor deposition, exemplify Compound I-28 while maintaining the reduced pressure. Compound II-21 is deposited to a thickness of 40 nm at a weight ratio of 50:50 and an overall deposition rate of 0.15 to 0.20 nm / sec,
It was a light emitting layer. Further, an electron transport layer as in Example 1,
An electron injecting electrode and a protective electrode were formed to obtain an organic EL device.
【００８３】このようにして得られた有機ＥＬ素子に対
して、実施例１と同様の特性評価を行ったところ、６．
１V 、１０mA/cm2 で６７１cd/m2 の発光（発光極大波
長λmax ＝４６５nm、色度座標（x,y）=（０．１５，
０．３３）が確認された。The organic EL device thus obtained was subjected to the same characteristic evaluation as in Example 1.
1V, 10mA / cm 2 emission of 671cd / m 2 by (emission maximum wavelength .lambda.max = 465 nm, the chromaticity coordinates (x, y) = (0.15 ,
0.33) was confirmed.
【００８４】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度３１３０cd
/m2 で、輝度半減時間は３１０時間の寿命特性を示し
た。When a constant current of 50 mA / cm 2 was passed through the device to continuously emit light, the initial luminance was 3130 cd.
At / m 2 , the luminance half life was 310 hours.
【００８５】＜比較例１＞実施例１と同様に、ＩＴＯ付
きガラス基板の洗浄、ホール注入層、輸送層の蒸着成膜
を行った後、減圧を保ったまま、例示化合物Ｉ−２８を
蒸着速度０．１５〜０．２０nm/secで４０nmの厚さに蒸
着し、発光層とした。さらに、実施例１と同様に電子輸
送層、電子注入電極、保護電極の成膜を行って、有機Ｅ
Ｌ素子を得た。<Comparative Example 1> In the same manner as in Example 1, after cleaning the glass substrate with ITO and depositing a hole injection layer and a transport layer by vapor deposition, Exemplified Compound I-28 was deposited while maintaining the reduced pressure. Evaporation was performed at a rate of 0.15 to 0.20 nm / sec to a thickness of 40 nm to form a light emitting layer. Further, an electron transport layer, an electron injection electrode, and a protective electrode were formed in the same manner as in Example 1, and organic
An L element was obtained.
【００８６】このようにして得られた有機ＥＬ素子に対
して、実施例１と同様の特性評価を行ったところ、６．
０V 、１０mA/cm2 で１７８cd/m2 の発光（発光極大波
長λmax ＝４３５nm、色度座標（x,y）=（０．１６，
０．１０）が確認された。The organic EL device thus obtained was subjected to the same characteristic evaluation as in Example 1.
0V, 10mA / cm 2 emission of 178cd / m 2 by (emission maximum wavelength .lambda.max = 435 nm, the chromaticity coordinates (x, y) = (0.16 ,
0.10) was confirmed.
【００８７】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度７４０cd/m
２で、輝度半減時間は１００時間の寿命特性を示した。When a constant current of 50 mA / cm 2 was passed through the device to continuously emit light, the initial luminance was 740 cd / m 2.
In No. 2 , the luminance half life showed a life characteristic of 100 hours.
【００８８】＜比較例２＞実施例１と同様に、ＩＴＯ付
きガラス基板の洗浄、ホール注入層、輸送層の蒸着成膜
を行った後、減圧を保ったまま、例示化合物II−２１を
蒸着速度０．１５〜０．２０nm/secで４０nmの厚さに蒸
着し、発光層とした。さらに、実施例１と同様に電子輸
送層、電子注入電極、保護電極の成膜を行って、有機Ｅ
Ｌ素子を得た。Comparative Example 2 In the same manner as in Example 1, after cleaning the glass substrate with ITO and depositing the hole injection layer and the transport layer by vapor deposition, Exemplified Compound II-21 was deposited while maintaining the reduced pressure. Evaporation was performed at a rate of 0.15 to 0.20 nm / sec to a thickness of 40 nm to form a light emitting layer. Further, an electron transport layer, an electron injection electrode, and a protective electrode were formed in the same manner as in Example 1, and the organic E layer was formed.
An L element was obtained.
【００８９】このようにして得られた有機ＥＬ素子に対
して、実施例１と同様の特性評価を行ったところ、５．
９V 、１０mA/cm2 で５２１cd/m2 の発光（発光極大波
長λmax ＝４６５nm、色度座標（x,y）=（０．１８，
０．３３）が確認された。The organic EL device thus obtained was evaluated for characteristics in the same manner as in Example 1.
9V, 10mA / cm 2 emission of 521cd / m 2 by (emission maximum wavelength .lambda.max = 465 nm, the chromaticity coordinates (x, y) = (0.18 ,
0.33) was confirmed.
【００９０】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度２５００cd
/m2 で、輝度半減時間は１４０時間の寿命特性を示し
た。When a constant current of 50 mA / cm 2 was passed through the device to continuously emit light, the initial luminance was 2500 cd.
At / m 2 , the luminance half-life exhibited a lifetime of 140 hours.
【００９１】[0091]
【発明の効果】本発明の有機ＥＬ素子は、青色の領域に
おいて低濃度での精密なドーピングを行うことなく混合
発光層のみで十分な効率と、実用に耐えうる発光寿命、
さらには広い製造マージンを持ち、しかも、バイポーラ
型混合層を用いたＥＬ素子に比べると駆動電圧を低く抑
えることが可能な有用な素子である。The organic EL device of the present invention has a sufficient efficiency and a luminous life that can withstand practical use with only the mixed luminous layer without performing precise doping at a low concentration in the blue region.
Further, it is a useful element having a wide manufacturing margin and capable of suppressing a driving voltage lower than that of an EL element using a bipolar type mixed layer.
【図１】本発明のＥＬ素子の構成例を示す断面図であ
る。FIG. 1 is a cross-sectional view illustrating a configuration example of an EL element of the present invention.
１ 有機ＥＬ素子 ２ 基板 ３ 陽極 ４ ホール注入輸送層 ５ 発光層 ６ 電子注入輸送層 ７ 陰極 DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Substrate 3 Anode 4 Hole injection / transport layer 5 Light emitting layer 6 Electron injection / transport layer 7 Cathode
フロントページの続き (72)発明者 斉藤 伸郎 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内 (72)発明者 青谷 淳司 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内 (72)発明者 井上 鉄司 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内 Ｆターム(参考） 3K007 AB00 AB04 AB06 AB18 BB06 CA01 CB01 DA00 DB03 EB00 FA01 Continuation of the front page (72) Inventor Nobuo Saito 1-13-1, Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Junji 1-13-1, Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Tetsuji Inoue 1-13-1, Nihonbashi, Chuo-ku, Tokyo F-term in TDK Corporation (reference) 3K007 AB00 AB04 AB06 AB18 BB06 CA01 CB01 DA00 DB03 EB00 FA01
Claims (9)
ン誘導体と下記化２で表されるフェニルアントラセン誘
導体のそれぞれ少なくとも一種以上を同時に含有する、
少なくとも１層の有機化合物混合層を有する有機ＥＬ素
子。 【化１】 【化２】 〔化１において、Ｒ1 およびＲ2 は、各々アルキル基、
シクロアルキル基、アリール基、アルケニル基、アルコ
キシ基、アリーロキシ基、アミノ基または複素環基を表
し、これらは同一でも異なるものであってもよい。ｒ１
およびｒ２は、各々、０または１〜５の整数を表す。ｒ
１およびｒ２が、各々、２以上の整数であるとき、Ｒ1
同士およびＲ2 同士は各々同一でも異なるものであって
もよく、Ｒ 1 同士またはＲ2 同士は結合して環を形成し
てもよい。化２において、Ｒ3 およびＲ4 は、各々アル
キル基、シクロアルキル基、アリール基、アルケニル
基、アルコキシ基、アリーロキシ基、アミノ基または複
素環基を表し、これらは同一でも異なるものであっても
よい。ｒ３およびｒ４は、各々、０または１〜５の整数
を表す。ｒ３およびｒ４が、各々、２以上の整数である
とき、Ｒ3 同士およびＲ4 同士は各々同一でも異なるも
のであってもよく、Ｒ 3 同士またはＲ4 同士は結合して
環を形成してもよい。〕1. A phenylanthrace represented by the following formula 1.
Derivative and phenylanthracene induction
Simultaneously containing at least one or more of each of the conductors,
Organic EL device having at least one organic compound mixed layer
Child. Embedded imageEmbedded image[In the chemical formula 1, R1 And RTwo Is an alkyl group,
Cycloalkyl group, aryl group, alkenyl group, alcohol
Shows a xy, aryloxy, amino or heterocyclic group.
However, they may be the same or different. r1
And r2 represent 0 or an integer of 1 to 5, respectively. r
When 1 and r2 are each an integer of 2 or more, R1
Each other and RTwo Each other is the same but different
Well, R 1 Each other or RTwo Join together to form a ring
You may. In the chemical formula 2, RThree And RFour Are each
Kill group, cycloalkyl group, aryl group, alkenyl
Group, alkoxy group, aryloxy group, amino group or
Represents a cyclic group, which may be the same or different
Good. r3 and r4 are each 0 or an integer of 1 to 5
Represents r3 and r4 are each an integer of 2 or more
When RThree Each other and RFour Each other is the same or different
May be R Three Each other or RFour Join together
A ring may be formed. ]
ン誘導体と下記化４で表されるフェニルアントラセン誘
導体のそれぞれ少なくとも一種以上を同時に含有する、
少なくとも１層の有機化合物混合層を有する有機ＥＬ素
子。 【化３】 【化４】 〔化３において、Ｒ51 およびＲ52 は、各々アルキル
基、シクロアルキル基、アリール基、アルケニル基、ア
ルコキシ基、アリーロキシ基、アミノ基または複素環基
を表し、これらは同一でも異なるものであってもよい。
化４において、Ｒ53 およびＲ54 は、各々アルキル基、
シクロアルキル基、アリール基、アルケニル基、アルコ
キシ基、アリーロキシ基、アミノ基または複素環基を表
し、これらは同一でも異なるものであってもよい。 〕2. A phenylanthracene derivative represented by the following formula (3) and a phenylanthracene derivative represented by the following formula (4):
An organic EL device having at least one organic compound mixed layer. Embedded image Embedded image [In the formula 3, R 51 and R 52 each represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group. Is also good.
In the chemical formula 4, R 53 and R 54 are each an alkyl group,
Represents a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, which may be the same or different. ]
2 、Ｒ3 およびＲ4 がアリール基である請求項１の有機
ＥＬ素子。3. R 1 and R in the above formulas 1 and 2
2. The organic EL device according to claim 1, wherein 2 , R 3 and R 4 are aryl groups.
52 、Ｒ53 およびＲ5 4 がアリール基である請求項２の
有機ＥＬ素子。4. R 51 and R in the above formulas 3 and 4
52, R 53 and R 5 4 is the organic EL device according to claim 2 is an aryl group.
ン誘導体と化２で表されるフェニルアントラセン誘導体
とをそれぞれ９５：５〜２０：８０wt％含有する請求項
１または３の有機ＥＬ素子。5. The organic EL device according to claim 1, comprising 95: 5 to 20:80 wt% of the phenylanthracene derivative represented by the chemical formula 1 and the phenylanthracene derivative represented by the chemical formula 2, respectively.
ン誘導体と化４で表されるフェニルアントラセン誘導体
とをそれぞれ９５：５〜２０：８０wt％含有する請求項
２または４の有機ＥＬ素子。6. The organic EL device according to claim 2, comprising 95: 5 to 20:80 wt% of the phenylanthracene derivative represented by the chemical formula 3 and the phenylanthracene derivative represented by the chemical formula 4, respectively.
求項１〜６のいずれかの有機ＥＬ素子。7. The organic EL device according to claim 1, wherein the organic compound mixed layer is a light emitting layer.
と、少なくとも１層のホール輸送層と、少なくとも１層
の電子注入輸送層とを有する請求項１〜７のいずれかの
有機ＥＬ素子。8. The organic EL device according to claim 1, further comprising at least one hole injection layer, at least one hole transport layer, and at least one electron injection transport layer.
と、少なくとも１層のホール輸送層と、少なくとも１層
の電子輸送層と、少なくとも１層の電子注入層とを有す
る請求項１〜８のいずれかの有機ＥＬ素子。9. The method according to claim 1, further comprising at least one hole injection layer, at least one hole transport layer, at least one electron transport layer, and at least one electron injection layer. Any organic EL device.
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|---|---|---|---|
| JP2000002697A JP3970495B2 (en) | 2000-01-11 | 2000-01-11 | Organic EL device |
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| JP3970495B2 JP3970495B2 (en) | 2007-09-05 |
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