JP2795932B2 - Electroluminescence element - Google Patents
Electroluminescence elementInfo
- Publication number
- JP2795932B2 JP2795932B2 JP1289907A JP28990789A JP2795932B2 JP 2795932 B2 JP2795932 B2 JP 2795932B2 JP 1289907 A JP1289907 A JP 1289907A JP 28990789 A JP28990789 A JP 28990789A JP 2795932 B2 JP2795932 B2 JP 2795932B2
- Authority
- JP
- Japan
- Prior art keywords
- light
- light emitting
- emitting layer
- organic
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000005401 electroluminescence Methods 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims description 160
- 238000002347 injection Methods 0.000 claims description 49
- 239000007924 injection Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 132
- 239000010408 film Substances 0.000 description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000000758 substrate Substances 0.000 description 39
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 38
- 239000006185 dispersion Substances 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 25
- 238000000151 deposition Methods 0.000 description 20
- 230000008021 deposition Effects 0.000 description 19
- 230000005284 excitation Effects 0.000 description 19
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 19
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 18
- 239000004926 polymethyl methacrylate Substances 0.000 description 18
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 16
- 229910052738 indium Inorganic materials 0.000 description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 16
- 238000007740 vapor deposition Methods 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 229960000956 coumarin Drugs 0.000 description 9
- 235000001671 coumarin Nutrition 0.000 description 9
- VSSSHNJONFTXHS-UHFFFAOYSA-N coumarin 153 Chemical compound C12=C3CCCN2CCCC1=CC1=C3OC(=O)C=C1C(F)(F)F VSSSHNJONFTXHS-UHFFFAOYSA-N 0.000 description 8
- 239000007850 fluorescent dye Substances 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- -1 rhodamine compound Chemical class 0.000 description 8
- YXCKIFUUJXNFIW-UHFFFAOYSA-N 5-[4-(1,3-dioxo-2-benzofuran-5-yl)phenyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C2=CC=C(C=C2)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 YXCKIFUUJXNFIW-UHFFFAOYSA-N 0.000 description 7
- 230000005684 electric field Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- FIZIRKROSLGMPL-UHFFFAOYSA-N phenoxazin-1-one Chemical compound C1=CC=C2N=C3C(=O)C=CC=C3OC2=C1 FIZIRKROSLGMPL-UHFFFAOYSA-N 0.000 description 4
- UOMHBFAJZRZNQD-UHFFFAOYSA-N phenoxazone Natural products C1=CC=C2OC3=CC(=O)C=CC3=NC2=C1 UOMHBFAJZRZNQD-UHFFFAOYSA-N 0.000 description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 4
- BCASZEAAHJEDAL-PHEQNACWSA-N 1,4-bis[(e)-2-(4-methylphenyl)ethenyl]benzene Chemical compound C1=CC(C)=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=C(C)C=C1 BCASZEAAHJEDAL-PHEQNACWSA-N 0.000 description 3
- XXKRKYCPIGXMAM-UHFFFAOYSA-N 1-methyl-3-(2-phenylphenyl)benzene Chemical compound CC1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1 XXKRKYCPIGXMAM-UHFFFAOYSA-N 0.000 description 3
- YRITVODHCMDVSY-VEGPOJNRSA-N [(2r,3s,5r)-5-(6-aminopurin-9-yl)-2-(phosphonooxymethyl)oxolan-3-yl] [(2r,3s)-3-hydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl hydrogen phosphate Chemical compound O=C1NC(=O)C(C)=CN1C1O[C@H](COP(O)(=O)O[C@@H]2[C@H](O[C@H](C2)N2C3=NC=NC(N)=C3N=C2)COP(O)(O)=O)[C@@H](O)C1 YRITVODHCMDVSY-VEGPOJNRSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- HXWQJYVUJPBQEW-VAWYXSNFSA-N 1-phenyl-4-[(e)-2-(4-phenylphenyl)ethenyl]benzene Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1/C=C/C(C=C1)=CC=C1C1=CC=CC=C1 HXWQJYVUJPBQEW-VAWYXSNFSA-N 0.000 description 2
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 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 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- QKLPIYTUUFFRLV-YTEMWHBBSA-N 1,4-bis[(e)-2-(2-methylphenyl)ethenyl]benzene Chemical compound CC1=CC=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=CC=C1C QKLPIYTUUFFRLV-YTEMWHBBSA-N 0.000 description 1
- VAMIQMSIDPJJJD-UHFFFAOYSA-N 1,4-bis[2,2-bis(4-methylphenyl)ethenyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC(C=C1)=CC=C1C=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 VAMIQMSIDPJJJD-UHFFFAOYSA-N 0.000 description 1
- QWDNXOVVSWDZIV-UHFFFAOYSA-N 1,4-bis[2-(4-ethylphenyl)ethenyl]benzene Chemical compound C1=CC(CC)=CC=C1C=CC(C=C1)=CC=C1C=CC1=CC=C(CC)C=C1 QWDNXOVVSWDZIV-UHFFFAOYSA-N 0.000 description 1
- VERMWGQSKPXSPZ-BUHFOSPRSA-N 1-[(e)-2-phenylethenyl]anthracene Chemical class C=1C=CC2=CC3=CC=CC=C3C=C2C=1\C=C\C1=CC=CC=C1 VERMWGQSKPXSPZ-BUHFOSPRSA-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
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008425 anthrones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229940083761 high-ceiling diuretics pyrazolone derivative Drugs 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 238000013208 measuring procedure Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 229960003540 oxyquinoline Drugs 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
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940043267 rhodamine b Drugs 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
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 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
- 239000001018 xanthene dye Substances 0.000 description 1
Classifications
-
- Y02B20/181—
Landscapes
- Electroluminescent Light Sources (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はエレクトロルミネッセンス素子に関し、詳し
くは比較的安価で容易に作製でき、波長範囲が広く、青
緑色から赤色までの可視光が得られるエレクトロルミネ
ッセンス素子に関する。Description: TECHNICAL FIELD The present invention relates to an electroluminescence device, and more particularly, to an electroluminescence device which is relatively inexpensive and can be easily manufactured, has a wide wavelength range, and can obtain visible light from blue-green to red. It relates to a luminescence element.
エレクトロルミネッセンス素子（以下EL素子という）
は、自己発光のため視認性が高く、また完全固体素子で
あるため耐衝撃性に優れるという特徴を有しており、現
在、無機，有機化合物を発光層に用いた様々なEL素子が
提案され、実用化が試みられている。また、電場発光と
それを励起光として用いる蛍光材料とを併用した構成の
発光素子が提案されており、下記の如き技術が開発され
ている。Electroluminescence device (hereinafter referred to as EL device)
Is characterized by high visibility due to self-luminescence and excellent impact resistance because it is a completely solid-state device. Currently, various EL devices using inorganic and organic compounds for the light-emitting layer have been proposed. Has been attempted for practical use. Further, a light-emitting element having a configuration using both electroluminescence and a fluorescent material using the electroluminescence as excitation light has been proposed, and the following techniques have been developed.
例えば、特開昭60−25195号公報、同60−170194号公
報，同61−51796号公報には、青緑色に発光する無機EL
材料（例えばZnS:CaCl,ZnS:CuMn等）とローダミン系の
蛍光色素との混合物を発光層として用い、白色発光を得
るEL素子が提案されている。これらの提案によると、EL
材料と蛍光色素を混合しているため、変換光を発生する
蛍光材料の交換が容易にできないという問題がある。ま
た常に励起光としての青緑色のEL発光が混ざるため、色
が白色化し、色変換素子としては不適当である。また、
色度的に純粋な白色が得られない等の問題がある。For example, JP-A-60-25195, JP-A-60-170194 and JP-A-61-51796 disclose inorganic EL emitting blue-green light.
An EL device that emits white light by using a mixture of a material (for example, ZnS: CaCl, ZnS: CuMn, etc.) and a rhodamine-based fluorescent dye as a light-emitting layer has been proposed. According to these proposals, EL
Since the material and the fluorescent dye are mixed, there is a problem that the fluorescent material generating the converted light cannot be easily exchanged. In addition, since blue-green EL emission as excitation light is always mixed, the color becomes white, which is unsuitable as a color conversion element. Also,
There is a problem that pure white color cannot be obtained.
また特開昭60−220597号公報には、交流電界を印加し
てピーク波長460〜520mmの範囲で発光する電界発光蛍光
体（例えばZnS:CaCl系の無機EL材料）とピーク波長590
〜610mmの範囲で発光する波長変換蛍光体（具体的にク
マリン，ローダミン系化合物）とを併用したものが提案
されている。この提案では、両者を混合して単一の発光
層とするもの、両者を積層して陽，陰電極間に介在され
るもの、あるいは全くEL素子構成の外部に波長変換体を
積層したものの三種類について言及している。しかし、
この技術では、EL素子として交流電界印加型の無機材料
を用いており、波長範囲が限定されているため発光色を
多彩に変化させることができなかった。さらに欧州特許
公開0281381号公報によれば、８−ヒドロキシキノリン
などの有機EL材料をホスト物質（host material）と、
クマリン系化合物等の波長変換蛍光材料をゲスト物質
（guest material）として、両者から形成された発光層
を正孔注入層の上に積層する構成である。有機EL材料か
ら成る発光層に微量（１モル％以下程度）の蛍光材料を
ドープすることにより赤から緑色にかけての高輝度発光
を得ている。この発明では、波長変換機構もただ単にホ
ストの発光をゲストが吸収し発光すると言うものでな
く、ホスト物質からゲスト物質へのエネルギー移動の結
果（J.Appl.Phys.65.3610（1989））である。この機構
によると確かに高い発光効率が得られているが、ホスト
物質の発光波長が緑色のため、得られる発光波長は赤色
から緑色の長波長光に限られている。ゲスト物質をホス
ト物質中へ極く微量ドープしなければならないので、発
光層作製がむずかしく、またゲスト物質を交換すること
が困難なため、変換色を容易に変えられないという欠点
がある。また、エネルギー移動を用いるためホストとゲ
ストは密着している（ホスト中にゲストを分散する）必
要があるなどの問題があった。JP-A-60-220597 discloses an electroluminescent phosphor (for example, ZnS: CaCl-based inorganic EL material) which emits light in the range of a peak wavelength of 460 to 520 mm when an AC electric field is applied, and a peak wavelength of 590.
A combination using a wavelength conversion phosphor (specifically, a coumarin or rhodamine compound) which emits light in a range of up to 610 mm has been proposed. In this proposal, there are three types: a mixture of the two to form a single light-emitting layer, a layer of both layers interposed between the positive and negative electrodes, or a layer of a wavelength converter outside the EL device configuration. Mention the type. But,
In this technique, an alternating-current electric field application type inorganic material is used as the EL element, and the emission color cannot be changed in various ways because the wavelength range is limited. Further, according to European Patent Publication 0281381, an organic EL material such as 8-hydroxyquinoline is used as a host material,
In this configuration, a wavelength conversion fluorescent material such as a coumarin compound is used as a guest material, and a light emitting layer formed from both is laminated on the hole injection layer. By emitting a small amount (about 1 mol% or less) of a fluorescent material into a light emitting layer made of an organic EL material, high-luminance light emission from red to green is obtained. In the present invention, the wavelength conversion mechanism does not mean that the guest simply absorbs light emitted from the host and emits light, but is the result of energy transfer from the host material to the guest material (J. Appl. Phys. 65.3610 (1989)). . According to this mechanism, a high luminous efficiency is certainly obtained, but the luminescent wavelength obtained is limited to a long wavelength light from red to green because the luminescent wavelength of the host material is green. Since a very small amount of the guest material must be doped into the host material, it is difficult to prepare the light emitting layer, and it is difficult to exchange the guest material, so that the conversion color cannot be easily changed. In addition, there is a problem that the host and the guest need to be in close contact with each other (the guest is dispersed in the host) because energy transfer is used.
また、特開昭57−51781号公報（特公昭64−7635号公
報）では、有機EL素子において発光帯域が２つの発光体
を有し、その第二発光体が第一発光体から放射される光
の波長を変化させることが可能なものが提案されてい
る。In Japanese Patent Application Laid-Open No. 57-51781 (Japanese Patent Publication No. 64-7635), an organic EL device has two luminous bodies having two luminous bands, and the second luminous body is radiated from the first luminous body. Devices capable of changing the wavelength of light have been proposed.
具体的に開示された例によれば、第一発光体として
は、テトラフェニルブタジエンのポリスチレン分散膜、
第二発光体としては、ペリレン系化合物の蒸着膜を用い
ている。第一発光体だけでは、ピーク波長467mmの青色
発光であるが、これに第二発光体を付与することによ
り、発光波長がピーク810mmの近赤外光へシフトさせて
いる。しかし、変換光が可視光でなく、また第二発光体
は第一発光体からの励起状態のエネルギー移動により発
光している。したがって、第一及び第二発光体の膜厚を
1000Å程度と薄くして第二発光体を密着させることが必
要である。さらに、蛍光材料部を交換し発光色を変える
ことが不可能である等の問題があった。According to the specifically disclosed example, as the first luminous body, a polystyrene dispersed film of tetraphenylbutadiene,
As the second luminous body, a vapor-deposited film of a perylene-based compound is used. The first light-emitting body alone emits blue light with a peak wavelength of 467 mm, but by adding a second light-emitting body, the light-emitting wavelength is shifted to near-infrared light with a peak of 810 mm. However, the converted light is not visible light, and the second luminous body emits light due to energy transfer in the excited state from the first luminous body. Therefore, the thickness of the first and second luminous bodies is reduced.
It is necessary to make the second luminous body closely contacted by making it as thin as about 1000 mm. Further, there is a problem that it is impossible to change the emission color by replacing the fluorescent material part.
また、本発明者は、発光層で蛍光材をドープし又は蛍
光層を密着させて作製された上記の有機EL素子において
は、無機EL素子の場合とは異なり、有機EL材料部におけ
る正孔と電子との再結合による発光が蛍光材に阻害さ
れ、その結果として発光効率が低減するという問題があ
ることを知見した。すなわち、一般に無機EL素子の場合
は、電流注入型でなく交流電圧駆動型であるため、蛍光
材料は発光材料との間で電荷の授受はないので、蛍光材
を電極間に配置するか又は電極外に配置するかで発光効
率への影響はみられないが、一方、有機EL素子において
は、蛍光材のエネルギーギャップが発光材のそれより小
さく選択されるために、蛍光材は正孔と電子の少なくと
も一方を捕捉するトラップとして作用し、これが、有機
EL素子特有の現象として発光効率を低減させる原因にな
るものと考えられる。Further, the present inventor, in the above-mentioned organic EL element produced by doping a fluorescent material in the light emitting layer or by closely attaching the fluorescent layer, unlike the case of the inorganic EL element, the hole in the organic EL material portion and It has been found that there is a problem that the emission of light due to recombination with electrons is inhibited by the fluorescent material, and as a result, the emission efficiency is reduced. That is, in general, in the case of an inorganic EL element, the fluorescent material is not an electric current injection type but an AC voltage drive type, so that no charge is transferred between the fluorescent material and the light emitting material. There is no effect on the luminous efficiency depending on the location of the phosphor, but on the other hand, in the organic EL device, since the energy gap of the phosphor is selected to be smaller than that of the luminescent material, the fluorescent material uses holes and electrons. Act as a trap to capture at least one of
This phenomenon is considered to be a cause peculiar to the EL element, which causes a reduction in luminous efficiency.
そこで、本発明者らは、上記の従来の技術の問題点を
解決し、また青緑色ないし赤色の発光を得、さらに白色
発光素子として使用できるEL素子を開発すべく鋭意研究
を重ねた。その結果、有機EL材料と波長変換蛍光材料を
組み合わせることによって、上記目的が達成できること
を見出した。本発明はかかる知見に基いて完成したもの
である。Therefore, the present inventors have intensively studied to solve the above-mentioned problems of the conventional technology, to obtain blue-green to red light emission, and to further develop an EL device that can be used as a white light-emitting device. As a result, they have found that the above object can be achieved by combining an organic EL material and a wavelength conversion fluorescent material. The present invention has been completed based on such findings.
すなわち、本発明は陽極と陰極との間に発光層を挟持
した有機エレクトロルミネッセンス材料部（以下、有機
EL材料部と記す）が、直流電圧あるいはパルス電圧を印
加して青色発光あるいは青緑色発光させる有機化合物を
含む発光材料からなる発光層を有すると共に、該有機EL
材料部の両電極間内部以外の位置に、前記発光層の発光
を吸収し青緑色から赤色までの少なくとも一つの色の可
視光の蛍光を発光する少なくとも一つの蛍光材料部を配
設してなるエレクトロルミネッセンス素子（EL素子）を
提供するものである。That is, the present invention provides an organic electroluminescent material section (hereinafter referred to as an organic electroluminescent material section) having a light emitting layer sandwiched between an anode and a cathode.
EL material section) has a light-emitting layer made of a light-emitting material containing an organic compound that emits blue light or blue-green light when a DC voltage or a pulse voltage is applied thereto.
At least one fluorescent material portion that absorbs light emitted from the light emitting layer and emits visible light fluorescence of at least one color from blue green to red is disposed at a position other than between the two electrodes of the material portion. An object is to provide an electroluminescence element (EL element).
本発明において、有機EL材料部は励起光を発光するも
の、即ち発光材料を含む層（発光層）を有するものであ
れば、形態については特に制限はない。本発明では青色
〜青緑色の短波長面発光が可能な有機EL素子を励起光源
として用いるため、従来の無機EL素子（青緑色より長波
長発光）と異なり波長変換用蛍光材料の選択幅が広が
り、より多くの波長変換光を得ることが可能となる。In the present invention, the form of the organic EL material portion is not particularly limited as long as it emits excitation light, that is, has a layer containing a light emitting material (light emitting layer). In the present invention, since an organic EL element capable of emitting light in a short wavelength range from blue to blue-green is used as an excitation light source, unlike conventional inorganic EL elements (emission of longer wavelength than blue-green), there is a wider range of choices of fluorescent materials for wavelength conversion. Thus, more wavelength converted light can be obtained.
本発明の有機EL材料部における発光材料は、有機化合
物であり、具体的には所望する色調により次のような化
合物が挙げられる。The light emitting material in the organic EL material part of the present invention is an organic compound, and specifically, the following compounds depending on a desired color tone.
（１）紫外域から紫色の励起光を得る場合 下記の一般式（Ｉ）で表される化合物が挙げられる。(1) When obtaining purple excitation light from the ultraviolet region The compound represented by the following general formula (I) is exemplified.
一般式（Ｉ）において ここでｎは2,3,4あるいは５である。また、 上記化合物のフェニル基，フェニレン基，ナフチル基
は炭素数１〜４のアルキル基，アルコキシ基，水酸基，
スルホニル基，カルボニル基，アミノ基，ジメチルアミ
ノ基あるいはジフェニルアミノ基等が単数または複数置
換したものであってもよい。また、これらは互いに結合
し、飽和５員環,6員環を形成してもよい。また、フェニ
ル基，フェニレン基，ナフチル基はパラ位で結合したも
のが、結合性が良く平滑な蒸着膜の形成のために好まし
い。具体的には以下の化合物である。 In the general formula (I) Here, n is 2, 3, 4, or 5. Also, The phenyl group, phenylene group and naphthyl group of the above compound are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyl group,
It may have one or more sulfonyl, carbonyl, amino, dimethylamino or diphenylamino groups. Further, these may be bonded to each other to form a saturated 5- or 6-membered ring. A phenyl group, a phenylene group, and a naphthyl group bonded in the para position are preferable for forming a smooth vapor-deposited film having good bonding properties. Specifically, they are the following compounds.
特に、ｐ−クォーターフェニル誘導体,p−クィンクフ
ェニル誘導体が好ましい。 In particular, p-quarter phenyl derivatives and p-quin phenyl derivatives are preferred.
（２）青色あるいは青緑色の励起光を得る場合 以下のスチルベン系化合物及びクマリン系化合物が挙
げられる。また、欧州特許公開0281381号公報に示され
る化合物等を用いてもよい。(2) When obtaining blue or blue-green excitation light The following stilbene-based compounds and coumarin-based compounds are exemplified. Further, compounds and the like shown in European Patent Publication No. 0281381 may be used.
（ア）一般式（II）て表されるスチルベン系化合物。(A) Stilbene compounds represented by the general formula (II).
（式中X1,X2,X3は、−Ｃ＝Ｃ−あるいは を示す。） 具体的には、以下の化合物が挙げられる。 (Where X 1 , X 2 , and X 3 represent —C ＝ C— or Is shown. The following compounds are specifically mentioned.
フェニレン基はオルト位，メタ位，パラ位のいずれで
結合してもよいが、一般には、結晶性が向上するために
はパラ位で結合したものが好ましい。 The phenylene group may be bonded at any of the ortho, meta, and para positions, but is generally preferably bonded at the para position in order to improve crystallinity.
（イ）一般式（III）で表されるクマリン系化合物 （式中R1,R2,R3,R4,R5,R6は各々に水素原子または炭素
数１〜４のアルキル基、R7は水素原子，素数１〜４のア
ルキル基またはフェニル基を示し、Ｘは−Ｓ−， を示し、Ｙは水素原子または を示す。(A) Coumarin compounds represented by the general formula (III) (Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 7 is a hydrogen atom, an alkyl group having a prime number of 1 to 4 or phenyl X represents -S-, And Y is a hydrogen atom or Is shown.
R8,R9は各々水素原子，メチル基，エチル基，あるい
はフェニル基であり、R4,R5,R6とR8,R9は互いに結合
し、飽和６員環を形成してもよい。さらにR1,R2,R3は互
いに結合し、飽和６員環を形成してもよい。） 具体的には以下の化合物が挙げられる。R 8 and R 9 are each a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and R 4 , R 5 , R 6 and R 8 , R 9 are bonded to each other to form a saturated 6-membered ring. Good. Further, R 1 , R 2 , and R 3 may combine with each other to form a saturated 6-membered ring. Specific examples include the following compounds.
本発明のEL素子において、上記有機EL材料部は、上記
の発光材料を含む発光層を有する構造であればよい。そ
の膜厚は、特に制限はなく適宜状況に応じて選定すれば
よいが、通常は5nm〜５μｍ程度とすればよい。また、
本発明の有機EL材料部の構成は各種の様態があるが、基
本的には二つの電極（陽極と陰極）に間に、上記発光層
を挟持した構成として、これに必要に応じて他層を介在
させればよい。具体的には、（１）陽極／発光層／陰
極，（２）陽極／正孔注入輸送層／発光層／陰極，
（３）陽極／正孔注入輸送層／発光層／電子注入輸送層
／陰極などの構成がある。なお、これらのEL材料部は、
支持基板上に形成することが好ましい。また、各種のフ
ィルター層を設けることもできる。 In the EL device of the present invention, the organic EL material portion may have a structure having a light emitting layer containing the above light emitting material. The film thickness is not particularly limited and may be appropriately selected according to the situation, but is usually about 5 nm to 5 μm. Also,
The configuration of the organic EL material section of the present invention has various modes. Basically, the above-mentioned light emitting layer is sandwiched between two electrodes (anode and cathode), and if necessary, other layers may be formed. May be interposed. Specifically, (1) anode / light emitting layer / cathode, (2) anode / hole injection / transport layer / light emitting layer / cathode,
(3) There are configurations such as anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode. In addition, these EL material parts
Preferably, it is formed on a supporting substrate. Further, various filter layers can be provided.
本発明のEL材料部における発光層は、以下の三つの機
能を併せ持つものである。即ち、注入機能 電界印加時に、陽極又は正孔注入輸送層より正孔を注
入することができ、陰極又は電子注入輸送層より電子を
注入することができる機能 輸送機能 注入した電荷（電子と正孔）を電界の力で移動させる
機能 発光機能 電子と正孔の再結合の場を提供し、これを発光につな
げる機能 但し、正孔の注入されやすさと電子の注入されやすさ
に違いがあってもよく、また正孔と電子の移動度で表わ
される輸送能に大小があってもよいが、どちらか一方の
電荷を移動することが好ましい。The light emitting layer in the EL material part of the present invention has the following three functions. In other words, when an electric field is applied, holes can be injected from the anode or the hole injection / transport layer, and electrons can be injected from the cathode or the electron injection / transport layer. Transport function Injected charges (electrons and holes) ) The function of moving the) by the force of an electric field. Light-emitting function Provides a field for recombination of electrons and holes, and connects it to light emission. However, there is a difference between the ease of hole injection and the ease of electron injection. Although the transport ability represented by the mobility of holes and electrons may be large or small, it is preferable to transfer either one of the charges.
上記の発光材料（発光層）は電子，正孔の輸送機能も
すぐれている。さらに固体状態の蛍光性が強いため、再
結合時に形成された上記化合物，その会合体または結晶
等の励起状態を光に変換する能力が大きい。The above-mentioned light-emitting material (light-emitting layer) has an excellent function of transporting electrons and holes. Further, since the solid-state fluorescence is strong, the ability to convert the excited state of the above-mentioned compound, its aggregate or crystal formed at the time of recombination into light is large.
本発明のEL素子において使用できる基板は、透明性を
有するものが好ましく、一般にガラス，透明プラスチッ
ク，石英等が充当される。また、電極（陽極，陰極）と
しては、金，アルミニウム，インジウム，マグネシウ
ム，銅，銀などの金属，これらの合金．混合物、特開昭
63−295695号公報に開示されている合金または混合物電
極、インジウムチンオキサイド（酸化インジウムと酸化
錫の混合酸化物;ITO）,SnO3,ZnO等の透明電極等が挙げ
られる。これらの中で素子の駆動電圧を低くできるた
め、特開昭63−295695号公報に開示されている合金また
は混合物電極、ITO,SnO3,ZnO等の透明電極等が好まし
い。なお陽極には、仕事関数の大きい金属または電気伝
導性化合物が好適であり、また陰極には、仕事関数の小
さい金属または電気伝導性化合物が好適である。これら
の電極は、少なくとも一方が透明あるいは半透明である
と、発光を透過し取り出す効率が良いため好ましい。The substrate that can be used in the EL device of the present invention is preferably a substrate having transparency, and generally, glass, transparent plastic, quartz, or the like is applied. The electrodes (anode, cathode) include metals such as gold, aluminum, indium, magnesium, copper, and silver, and alloys thereof. Mixture, JP
63-295695 discloses an alloy or mixture electrode, a transparent electrode such as indium tin oxide (mixed oxide of indium oxide and tin oxide; ITO), SnO 3 , ZnO and the like. Among them, alloy or mixture electrodes disclosed in JP-A-63-295695, and transparent electrodes such as ITO, SnO 3 , ZnO, etc. are preferable because the driving voltage of the element can be lowered. A metal with a high work function or an electrically conductive compound is suitable for the anode, and a metal or an electrically conductive compound with a small work function is suitable for the cathode. It is preferable that at least one of these electrodes is transparent or translucent, because the efficiency of transmitting and extracting light is good.
前述した（１）陽極／発光層／陰極よりなる構成の有
機EL材料部（EL素子部）を作成するには、例えば次の如
き手順にしたがえばよい。即ち、まず、基板上に電極を
蒸着もしくはスパッタ法にて製膜する。この際、膜状の
電極の膜厚は、一般に10nm〜１μｍ、特に200nm以下
が、発光の透過率を高める上で好ましい。次に、この電
極の上に発光材料を、薄膜状に形成して発光層とする。
発光材料の薄膜化方法は、スピンコート，キャスト，蒸
着法等があるが、均一な膜が得やすいこと、及びピンホ
ールが生成しないことから、とりわけ蒸着法が好まし
い。発光材料の薄膜化に際して蒸着法を採用する場合、
その蒸着の条件は使用する化合物の種類、分子堆積膜の
目的とする分子構造，会合構造等により異なり、特に定
めることは出来ないが、例えばボート加熱温度50〜400
℃、真空度10-2〜10-6Pa、蒸着速度0.01〜50nm/秒、基
板温度−50〜＋300℃の範囲で膜厚5nm〜５μｍとなるよ
うに選定すればよい。特にボート加熱温度は化合物が分
解しない温度にすることが好ましい。この薄膜形成後、
対向電極を蒸着法やスパッタ法にて膜厚50〜200nmで形
成すれば、EL素子として作用する有機EL材料部が作製さ
れる。In order to prepare the above-mentioned (1) organic EL material part (EL element part) composed of the anode / light-emitting layer / cathode, for example, the following procedure may be performed. That is, first, an electrode is formed on a substrate by vapor deposition or sputtering. At this time, the thickness of the film-like electrode is generally 10 nm to 1 μm, and particularly preferably 200 nm or less, in order to increase the transmittance of light emission. Next, a light emitting material is formed in a thin film on the electrode to form a light emitting layer.
The light-emitting material can be made into a thin film by spin coating, casting, vapor deposition, or the like, but vapor deposition is particularly preferred because a uniform film is easily obtained and pinholes are not generated. When using a vapor deposition method when thinning a luminescent material,
The conditions for the deposition vary depending on the type of the compound used, the intended molecular structure of the molecular deposition film, the association structure, and the like, and cannot be particularly defined.
C., a degree of vacuum of 10.sup.- 2 to 10.sup.-6 Pa, a deposition rate of 0.01 to 50 nm / sec, and a substrate temperature of -50 to + 300.degree. In particular, the boat heating temperature is preferably a temperature at which the compound does not decompose. After forming this thin film,
If the counter electrode is formed to a thickness of 50 to 200 nm by a vapor deposition method or a sputtering method, an organic EL material portion acting as an EL element is manufactured.
また、（２）陽極／正孔注入輸送層／発光層／陰極の
構成の有機EL材料部を作製するには、まず電極を上記
（１）のEL材料部と同様に形成し、その後、正孔注入材
料（正孔伝達化合物）を電極上に蒸着法で薄膜化して正
孔注入輸送層を形成する。この際の蒸着条件は、前記発
光材料の薄膜形成の蒸着条件に準じればよい。その後は
上記（１）のEL材料部を作成する場合と同様に、発光材
料の薄膜形成及び対向電極の形成を行えば、所望する上
記（２）の構成の有機EL材料部が作製される。なお、こ
の（２）の構成のEL素子において、正孔注入輸送層と発
光層の作製順序を逆にし、電極／発光層／正孔注入輸送
層／電極の順に作製することも可能である。In order to prepare (2) an organic EL material portion having the structure of anode / hole injection / transport layer / light emitting layer / cathode, first, an electrode is formed in the same manner as in the above-mentioned (1) EL material portion, and then the positive electrode is formed. A hole injecting material (hole transporting compound) is thinned on an electrode by an evaporation method to form a hole injecting and transporting layer. The vapor deposition conditions at this time may be in accordance with the vapor deposition conditions for forming the thin film of the light emitting material. After that, as in the case of forming the EL material part in the above (1), by forming a thin film of the light emitting material and forming the counter electrode, the desired organic EL material part having the structure of the above (2) is manufactured. In the EL device having the configuration (2), it is also possible to reverse the manufacturing order of the hole injecting and transporting layer and the light emitting layer, and manufacture them in the order of electrode / light emitting layer / hole injecting and transporting layer / electrode.
さらに、（３）陽極／正孔注入輸送層／発光層／電子
注入輸送層／陰極の構成の有機EL材料部を作成するに
は、まず電極を上記（１）のEL材料部と同様に形成し、
その後、正孔注入輸送層を上記（２）のEL材料部と同様
に形成し、その上から上記（１）のEL材料部を作製する
場合と同様に、発光材料の薄膜を形成する。しかる後
に、電子注入材料（電子伝達化合物）を蒸着法にて薄膜
化することにより、発光層上に電子注入輸送層を形成
し、最後に上記（１）のEL材料部を作製する場合と同様
に、対向電極を形成すれば、目的とする上記（３）の構
成のEL材料部が作成される。ここで、正孔注入輸送層／
発光層／電子注入輸送層の順序を、電子注入輸送層／発
光層／正孔注入輸送層に変えて、電極／電子注入輸送層
／発光層／正孔注入輸送層／電極の順に作製してもよ
い。Further, in order to prepare (3) an organic EL material portion having a constitution of anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode, first, an electrode is formed in the same manner as in the above-mentioned (1) EL material portion. And
Thereafter, a hole injecting / transporting layer is formed in the same manner as in the above-mentioned (2) EL material portion, and a thin film of a luminescent material is formed thereon in the same manner as in the case of producing the above-mentioned (1) EL material portion. Thereafter, the electron injection material (electron transfer compound) is thinned by an evaporation method to form an electron injection transport layer on the light emitting layer, and finally, the same as in the case of manufacturing the EL material part in the above (1). Then, if an opposing electrode is formed, an intended EL material portion having the above configuration (3) is formed. Here, the hole injection transport layer /
The order of the light emitting layer / the electron injection / transport layer was changed to the electron injection / transport layer / the light emitting layer / the hole injection / transport layer, and the electrode / electron injection / transport layer / the light emitting layer / the hole injection / transport layer / the electrode were formed in this order. Is also good.
なお、本発明のEL素子では、正孔注入輸送層や電子注
入輸送層は必ずしも必要ではないが、これらの層がある
と、発光性能が一段と向上する。ここで、正孔注入輸送
層（正孔注入層）は、正孔伝達化合物（正孔注入材料）
よりなり、陽極より注入された正孔を、発光層に伝達す
る機能を持つ。この層をEL素子の陽極と発光層間に挟む
ことにより低電圧でより多くの正孔が発光層に注入さ
れ、素子の輝度は向上する。In the EL device of the present invention, the hole injection / transport layer and the electron injection / transport layer are not always necessary, but the presence of these layers further improves the light emission performance. Here, the hole injection transport layer (hole injection layer) is a hole transport compound (hole injection material).
And has a function of transmitting holes injected from the anode to the light emitting layer. By sandwiching this layer between the anode of the EL element and the light emitting layer, more holes are injected into the light emitting layer at a low voltage, and the luminance of the element is improved.
ここで用いられる正孔注入輸送層の正孔伝達化合物
は、電場を与えられた二個の電極間に配置されて陽極か
ら正孔が注入された場合、正孔を適切に発光層へ伝達す
ることができる化合物である。正孔注入輸送層を陽極と
発光層との間に挟むことにより、より低い電界で多くの
正孔が発光層に注入される。さらに、陰極や電子注入輸
送層から発光層に注入された電子は、発光層と正孔層の
界面に存在する電子の障壁により、この発光層内の界面
付近に蓄積され発光効率が向上する。ここで好ましい正
孔伝達化合物は、104〜106ボルト/cmの電場を与えられ
た電極間に層が配置された場合、少なくとも10-6cm2/ボ
ルト・秒の正孔移動度をもつ。従って好ましい例として
は、光導電材料において正孔の電荷輸送材として用いら
れている各種化合物があげられる。The hole transport compound of the hole injection transport layer used here is disposed between two electrodes to which an electric field is applied, and when holes are injected from the anode, the holes are appropriately transmitted to the light emitting layer. Is a compound that can be By interposing the hole injection transport layer between the anode and the light emitting layer, many holes are injected into the light emitting layer with a lower electric field. Further, electrons injected from the cathode or the electron injection / transport layer into the light emitting layer are accumulated near the interface in the light emitting layer due to the electron barrier existing at the interface between the light emitting layer and the hole layer, and the light emission efficiency is improved. Preferred hole transport compounds here have a hole mobility of at least 10 -6 cm 2 / volt-second when the layer is placed between electrodes exposed to an electric field of 10 4 to 10 6 volts / cm. . Therefore, preferred examples include various compounds used as a hole charge transporting material in a photoconductive material.
このような電荷輸送材として以下のような例があげら
れる。Examples of such charge transport materials include the following.
米国特許第3112197号明細書等に記載されているトリ
アゾール誘導体、 米国特許第3189447号明細書等に記載されているオキ
サジアゾール誘導体、 特公昭37−16096号公報等に記載されているイミダゾ
ール誘導体、 米国特許第3615402号，同3820989号，同3542544号明
細書や特公昭45−555号，同51−10983号公報さらには特
開昭51−93224号，同55−17105号，同56−4148号，同55
−108667号，同55−156953号，同56−36656号公報等に
記載されているポリアリールアルカン誘導体、 米国特許第3180729号，同4278746号明細書や特開昭55
−88064号，同55−88065号，同49−105537号，同55−51
086号，同56−80051号，同56−88141号，同57−45545
号，同54−112637号，同55−74546号公報等に記載され
ているピラゾリン誘導体およびピラゾロン誘導体、 米国特許第3615404号明細書や特公昭51−10105号，同
46−3712号，同47−25336号公報さらには特開昭54−534
35号，同54−110536号，同54−119925号公報等に記載さ
れているフェニレンジアミン誘導体、 米国特許第3567450号，同3180703号，同3240597号，
同3658520号，同4232103号，同4175961号，同4012376号
明細書や特公昭49−35702号，同39−27577号公報さらに
は特開昭55−144250号，同56−119132号，同56−22437
号公報，西独特許第1110518号明細書等に記載されてい
るアリールアミン誘導体、 米国特許第3526501号明細書等に記載されているアミ
ノ置換カルコン誘導体、 米国特許第3257203号明細書等に記載されているオキ
サゾール誘導体、 特開昭56−46234号公報等に記載されているスチリル
アントラセン誘導体、 特開昭54−110837号公報等に記載されている 特開昭54−110837号公報等に記載されているフルオレ
ノン誘導体、 米国特許第3717462号明細書や特開昭54−59143号，同
55−52063号，同55−52064号，同55−46760号，同55−8
5495号，同57−11350号，同57−148749号公報等に記載
されているヒドラゾン誘導体、 特開昭61−210363号，同61−228451号，同61−14642
号，同61−72255号，同62−47646号，同62−36674号，
同62−10652号，同62−30255号，同60−93445号，同60
−94462号，同60−174749号，同60−175052号公報等に
記載されているスチルベン誘導体などを列挙することが
できる。Triazole derivatives described in U.S. Patent No. 3,112,197, etc., oxadiazole derivatives described in U.S. Patent No. 3,189,447, etc., imidazole derivatives described in JP-B-37-1696, etc. U.S. Patent Nos. 3615402, 3820989, 3542544, JP-B Nos. 45-555, 51-10983, and JP-A-51-93224, 55-17105, 56-4148. , Id 55
Polyarylalkane derivatives described in JP-A-108667, JP-A-55-156953, JP-A-56-36656 and the like; U.S. Patent Nos. 3,180,729 and 4,278,746;
-88064, 55-88065, 49-105537, 55-51
Nos. 086, 56-80051, 56-88141, 57-45545
Pyrazoline derivatives and pyrazolone derivatives described in U.S. Pat. Nos. 6,115,105, 54-112637, 55-74546, and the like.
46-3712, 47-25336 and JP-A-54-534.
Phenylenediamine derivatives described in JP-A Nos. 35, 54-110536 and 54-119925; U.S. Pat. Nos. 3,567,450, 3,180,703, 3,240,597;
Nos. 3,658,520, 4,322,103, 4,117,961 and 4,012,376, and JP-B-49-35702, JP-A-39-27577, and JP-A-55-144250, JP-A-56-119132, and JP-A-56-119. 22437
No. 3,085,086, an arylamine derivative described in West German Patent No. 1110518, an amino-substituted chalcone derivative described in US Pat. No. 3,235,501, and a US Pat. No. 3,257,203. Oxazole derivatives, styryl anthracene derivatives described in JP-A-56-46234, etc., and JP-A 54-110837 described in JP-A-54-110837, etc. Fluorenone derivatives, described in U.S. Pat. No. 3,717,462 and JP-A-54-59143,
55-52063, 55-52064, 55-46760, 55-8
Hydrazone derivatives described in JP-A-5495, JP-A-57-11350, JP-A-57-148749, etc., and JP-A-61-210363, JP-A-61-228451, JP-A-61-14642.
Nos. 61-72255, 62-47646, 62-36674,
No. 62-10652, No. 62-30255, No. 60-93445, No. 60
Stilbene derivatives and the like described in JP-A-94462, JP-A-60-174749, JP-A-60-175052 and the like can be listed.
さらに特に好ましい例としては、特開昭63−295695号
公報に開示されているホール輸送層としての化合物（芳
香族三級アミン）や正孔注入帯としての化合物（ポルフ
ィリン化合物）をあげることができる。More particularly preferred examples include a compound as a hole transport layer (aromatic tertiary amine) and a compound as a hole injection zone (porphyrin compound) disclosed in JP-A-63-295695. .
さらに特に正孔伝達化合物として好ましい例は、特開
昭53−27033号公報，同54−58445号公報，同54−149634
号公報，同54−64299号公報，同55−79450号公報，同55
−144250号公報，同56−119132号公報，同61−295558号
公報，同61−98353号公報及び米国特許第4127412号明細
書等に開示されているものである。それらの例を示せば
次の如くである。Further preferred examples of the hole transport compound are described in JP-A-53-27033, JP-A-54-58445, and JP-A-54-149634.
JP-A-54-64299, JP-A-55-79450, and 55
No. 144250, No. 56-119132, No. 61-295558, No. 61-98353, and U.S. Pat. No. 4,127,412. Examples of these are as follows.
これらの正孔伝達化合物から正孔注入輸送層を形成す
るが、この正孔注入層は一層からなってもよく、あるい
は上記一層と別種の化合物を用いた正孔注入輸送層を積
層してもよい。 A hole injecting and transporting layer is formed from these hole transporting compounds, and the hole injecting layer may be composed of a single layer, or may be formed by laminating a hole injecting and transporting layer using a different compound from the above layer. Good.
一方、電子注入輸送層（電子注入層）は電子を伝達す
る化合物よりなる。電気注入輸送層を形成する電子伝達
化合物（電子注入材料）の好ましい例には、 などのニトロ置換フルオレノン誘導体、 これらの正孔伝達化合物から正孔注入輸送層を形成す
るが、この正孔注入層は一層からなっても特開昭57−
149259号，同58−55450号，同63−104061号公報等に記
載されているアントラキノジメタン誘導体、Polymer
Preprints,Japan Vol.37,No.3（1988）,p.681等に記載
されている。On the other hand, the electron injection transport layer (electron injection layer) is made of a compound that transmits electrons. Preferred examples of the electron transfer compound (electron injection material) forming the electric injection transport layer include: A hole injecting and transporting layer is formed from these hole transporting compounds, and the hole injecting layer may be composed of a single layer.
Anthraquinodimethane derivatives described in 149259, 58-55450, 63-100401, etc., Polymer
Preprints, Japan Vol. 37, No. 3 (1988), p.
などのジフェニルキノン誘導体、 などのチオピランジオキシド誘導体、J.J.APPl.Phy
s.,27,L 269（1988）等に記載されている で表わされる化合物、 特開昭60−69657号，同61−143764号，同61−148159
号公報等に記載されているフレオレニリデンメタン誘導
体、 特開昭61−225151号，同61−233750号公報等に記載さ
れているアントラキノジメタン誘導体及びアントロン誘
導体などをあげることができる。 Diphenylquinone derivatives such as, Thiopyran dioxide derivatives such as JJAPPl.Phy
s., 27, L 269 (1988), etc. Compounds represented by the following formulas: JP-A-60-69657, JP-A-61-143764, JP-A-61-148159
And the anthraquinodimethane derivatives and anthrone derivatives described in JP-A Nos. 61-225151 and 61-233750.
以上の構成よりなる本発明の有機EL材料部は、直流を
加える場合、陽極を＋，陰極を−の極性として、電圧５
〜40Vを印加すれば発光する。逆の極性で電圧を印加し
ても電流は流れず発光しない。また、交流や任意のパル
ス電圧を印加することもでき、この場合陽極に＋，陰極
に−のバイアスの状態のときのみ発光する。In the organic EL material section of the present invention having the above-described configuration, when a direct current is applied, the anode has a positive polarity, the cathode has a negative polarity, and a voltage of 5
It emits light when ~ 40V is applied. Even if a voltage is applied with the opposite polarity, no current flows and no light is emitted. Alternatively, an AC or an arbitrary pulse voltage can be applied. In this case, light is emitted only when the anode has a positive bias and the cathode has a negative bias.
本発明における有機EL材料部は上記のようにして得ら
れる。The organic EL material part in the present invention is obtained as described above.
次いで本発明のおける蛍光材料部は、上記の有機EL材
料部に存在する発光層からの発光を吸収して、波長変換
できる蛍光色素を含有するものであればよい。Next, the fluorescent material part in the present invention may be any one that contains a fluorescent dye capable of absorbing the light emitted from the light emitting layer existing in the organic EL material part and converting the wavelength.
ここで、蛍光色素としては市販のレーザー色素等が好
ましいが、固体状態（樹脂中での分散状態を含む）で強
い蛍光性を有するものであれば、特に制限はない。Here, as the fluorescent dye, a commercially available laser dye or the like is preferable, but there is no particular limitation as long as it has strong fluorescence in a solid state (including a dispersed state in a resin).
具体的には紫外光から青色に変化する色素としては、
1,4−ビス（２−メチルスチリン）ベンゼン，トランス
−4,4′−ジフェニルスチルベンゼン等のスチルベンゼ
ン系色素,7−ヒドロキシ−４−メチルクマリン等のクマ
リン系色素が挙げられる。Specifically, as a dye that changes from ultraviolet light to blue,
Examples include stilbene-based dyes such as 1,4-bis (2-methylstyrin) benzene and trans-4,4'-diphenylstilbenzene, and coumarin-based dyes such as 7-hydroxy-4-methylcoumarin.
また、青色のEL光を励起光として緑色に変換する場合
は、2,3,5,6−1H,4H−テトラヒドロ−８−トリフロルメ
チルキノリジノ（9,9a,1−gh）クマリン（クマリン15
3）等のクマリン色素が挙げられる。When blue EL light is converted to green light as excitation light, 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolizino (9,9a, 1-gh) coumarin ( Coumarin 15
Coumarin dyes such as 3).
青色から緑色にかけての波長の励起光を吸収し、橙色
から赤色にかけての色へ変換す色素としては４−ジシア
ノメチレン−２−メチル−６−（ｐ−ジメチルアミノス
チルリン）−4H−ピラン（DCM）等のシアニン系色素,1
−エチル−２−（４−（ｐ−ジメチルアミノフェニル）
−1,3−ブタジエニル）−ピリジウム−パーコラレイト
（ピリジン１）等のピリジン系色素，ローダミンB,ロー
ダミン6G等のキサンテン系色素、他にオキサジン系が挙
げられる。As a dye that absorbs excitation light having a wavelength ranging from blue to green and converts it into a color ranging from orange to red, 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostillin) -4H-pyran (DCM ) And other cyanine dyes, 1
-Ethyl-2- (4- (p-dimethylaminophenyl)
Examples thereof include pyridine dyes such as [1,3-butadienyl) -pyridium-percolarate (pyridine 1), xanthene dyes such as rhodamine B and rhodamine 6G, and oxazine dyes.
この蛍光材料部は、上述に例示するような蛍光色素を
蒸着あるいはスパッタリング法で製膜された膜、適当な
樹脂を結着性樹脂としてその中に分散させた膜等いずれ
の形態であってもよい。膜厚はEL励起光を充分に吸収
し、蛍光を発生する機能を妨げるものでなければ制限は
なく、通常蛍光色素により若干異なるが100nm〜5mm程度
が適当である。This fluorescent material portion may be in any form, such as a film formed by depositing a fluorescent dye as described above by vapor deposition or sputtering, a film in which an appropriate resin is dispersed as a binding resin, and the like. Good. The thickness of the film is not limited as long as it does not interfere with the function of generating the fluorescence by sufficiently absorbing the EL excitation light, and usually varies slightly depending on the fluorescent dye, but is suitably about 100 nm to 5 mm.
ここで適当な樹脂を結着性樹脂としてその中に分散さ
せた膜、すなわち樹脂分散型の場合、蛍光色素の分散濃
度は、蛍光の濃度消光を起こすことがなく、かつ励起光
を充分に吸収できる範囲であれば良い。蛍光色素の種類
によるが、使用する結合樹脂に対して10-2〜10-4モル／
程度が適当である。Here, in the case of a film in which an appropriate resin is dispersed as a binder resin therein, that is, in the case of a resin dispersion type, the dispersion concentration of the fluorescent dye does not cause quenching of the concentration of the fluorescence and sufficiently absorbs the excitation light. What is necessary is just the range which can be performed. Depending on the type of fluorescent dye, 10 -2 to 10 -4 mole /
The degree is appropriate.
また、膜厚を調整することで、有機EL材料部の発光層
から発光される励起光の透過強度を変化させることがで
きる。膜厚を薄くすると蛍光材料部を通して見た光は、
EL励起光の透過成分と蛍光成分が混ざり白色光に近いも
のになる。膜厚を適当に調整すれば色度的に完全な白色
光を得ることも可能である。Further, by adjusting the film thickness, the transmission intensity of the excitation light emitted from the light emitting layer of the organic EL material portion can be changed. When the film thickness is reduced, the light seen through the fluorescent material part becomes
The transmission component and the fluorescence component of the EL excitation light are mixed to be close to white light. By adjusting the film thickness appropriately, it is possible to obtain chromatically perfect white light.
一方、膜厚を厚くするとEL透過成分が少なくなり、蛍
光成分のみの光を得ることが可能となる。On the other hand, when the film thickness is increased, the EL transmission component is reduced, and it becomes possible to obtain light of only the fluorescence component.
以上のようにして、本発明の蛍光材料部を得ることが
できる。As described above, the fluorescent material part of the present invention can be obtained.
本発明のEL素子は、上述の励起光を発光する有機EL材
料部及び変換光を発光する蛍光材料部からなるものであ
る。その構成は有機EL材料部で発光した励起光が減衰さ
れず、効率良く蛍光材料部に吸収され、かつ蛍光材料部
が発光した励起光が減衰されず、外部へ取り出せる構成
である必要がある。そのためには、蛍光材料部は有機EL
材料部の両電極間内部以外に存在させなければならな
い。具体的に例示すると次の如くである。The EL element of the present invention comprises the above-mentioned organic EL material part emitting the excitation light and the fluorescent material part emitting the converted light. It is necessary that the excitation light emitted from the organic EL material part is not attenuated, is efficiently absorbed by the fluorescent material part, and the excitation light emitted from the fluorescent material part is not attenuated and can be extracted to the outside. For that purpose, the fluorescent material part is organic EL
It must be present in the material portion other than between the two electrodes. Specific examples are as follows.
蛍光材料部を有機EL材料部の透明電極あるいは半透明
電極上に積層する。例えば、波長変換蛍光材料部／透明
あるいは半透明電極／発光層及び正孔，電子注入層／電
極／支持基板、あるいは電極／発光層及び正孔，電子注
入層／透明あるいは半透明電極／波長変換蛍光材料部／
透明支持基板の構成のEL素子が挙げられる。The fluorescent material part is laminated on the transparent electrode or the translucent electrode of the organic EL material part. For example, wavelength conversion fluorescent material portion / transparent or translucent electrode / light emitting layer and hole, electron injection layer / electrode / support substrate, or electrode / light emitting layer and hole, electron injection layer / transparent or translucent electrode / wavelength conversion Fluorescent material section /
An EL element having a configuration of a transparent support substrate may be used.
蛍光材料部を有機EL材料部と並列に横置する。例え
ば、電極／発光層及び正孔，電子注入層／電極の構成の
有機EL材料部の横に波長変換蛍光材料部を置き、この両
方を支持基板に存在させた素子が挙げられる。The fluorescent material section is placed in parallel with the organic EL material section. For example, there is an element in which a wavelength conversion fluorescent material portion is placed beside an organic EL material portion having a configuration of an electrode / light emitting layer and a hole / electron injection layer / electrode, and both of them are present on a support substrate.
蛍光材料部は有機EL材料部の透明支持基板内に分散、
あるいは透明支持基板上に積層させる。例えば、電極／
発光層及び電子，正孔注入層／透明あるいは半透明電極
／波長変換蛍光材料部が分散された支持基板、あるいは
波長変換蛍光材料部／透明支持基板／透明あるいは半透
明電極／発光層及び正孔，電子注入層／電極の構成のEL
素子が挙げられる。The fluorescent material part is dispersed in the transparent support substrate of the organic EL material part,
Alternatively, they are laminated on a transparent support substrate. For example, electrode /
Emitting layer and electron / hole injecting layer / transparent or translucent electrode / support substrate in which wavelength converting fluorescent material portion is dispersed, or wavelength converting fluorescent material portion / transparent supporting substrate / transparent or translucent electrode / light emitting layer and hole , EL with electron injection layer / electrode configuration
Element.
蛍光材料部は有機EL材料部の透明あるいは半透明電極
内に、導電率，電子あるいは正孔の注入効率等を著しく
低下させない範囲で分散させる。例えば、波長変換蛍光
材料部が分散された透明あるいは半透明電極／発光層及
び正孔，電子注入層／電極／支持基板、あるいは電極／
発光層及び正孔，電子注入層／波長変換蛍光材料部が分
散された透明あるいは半透明電極／透明支持基板の構成
のEL素子が挙げられる。なお、およびの構成では蛍
光材料部を容易に変換することができるものである。The fluorescent material portion is dispersed in the transparent or translucent electrode of the organic EL material portion within a range that does not significantly reduce the conductivity, the injection efficiency of electrons or holes, and the like. For example, a transparent or translucent electrode / light-emitting layer and holes, an electron injection layer / electrode / support substrate, or an electrode /
An EL device having a transparent or translucent electrode / transparent support substrate in which a light emitting layer and a hole / electron injection layer / wavelength conversion fluorescent material portion are dispersed is exemplified. In the configurations of and, the fluorescent material portion can be easily converted.
以上の如く本発明のEL素子の構成の態様が挙げられる
が、これらの構成に特に制限されるものではない。As described above, the embodiments of the configuration of the EL element of the present invention are mentioned, but the present invention is not particularly limited to these configurations.
本発明において、有機EL材料部の発光材料と蛍光材料
部の蛍光材料の組合せを変化させることにより、得られ
る可視光の色調を変化させることができる。In the present invention, the color tone of the obtained visible light can be changed by changing the combination of the light emitting material of the organic EL material part and the fluorescent material of the fluorescent material part.
次に本発明を実施例よりさらに詳しく説明する。 Next, the present invention will be described in more detail with reference to examples.
実施例１ （１）有機EL材料部の製造 25mm×75mm×1.1mmのガラス基板上にITOを蒸着法にて
100nmの厚さで製膜したものを透明支持基板とした（HOY
A製）。この透明支持基板を市販の蒸着装置（日本真空
技術（株）製）の基板ホルダーに固定しモリブデン製の
抵抗加熱ボートにN,N′−ジフェニル−N,N′−ビス−
（３−メチルフェニル）−〔1,1′ビフェニル〕−4,4′
−ジアミン（TPDA）を200mgを入れ、また別のモリブデ
ン製ボートに1,4−ビス（４−エチルスチリル）ベンゼ
ン（PESB）を200mg入れて真空槽を１×10-4Paまで減圧
した。Example 1 (1) Production of organic EL material section ITO was deposited on a 25 mm x 75 mm x 1.1 mm glass substrate by vapor deposition.
A film formed to a thickness of 100 nm was used as a transparent support substrate (HOY
A). This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N'-diphenyl-N, N'-bis- was added to a molybdenum resistance heating boat.
(3-methylphenyl)-[1,1'biphenyl] -4,4 '
200 mg of diamine (TPDA) was charged, and 200 mg of 1,4-bis (4-ethylstyryl) benzene (PESB) was charged into another molybdenum boat, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa.
その後TPDA入りの前記ボートを215〜220℃まで加熱
し、TPDAを蒸着速度0.1〜0.3nm/sで透明支持基板上に蒸
着して、膜厚80nmの正孔注入層を製膜させた。Thereafter, the boat containing TPDA was heated to 215 to 220 ° C., and TPDA was deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s to form a hole injection layer having a thickness of 80 nm.
この時の基板温度は室温であった。これを真空槽より
取り出すことなく、正孔注入層の上に、もう一つのボー
トよりPESBを発光層として80nm積層蒸着した。蒸着条件
はボート温度が220〜225℃で蒸着速度は0.3〜0.5nm/s,
基板温度は室温であった。The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, PESB was deposited as a light-emitting layer to a thickness of 80 nm from another boat on the hole injection layer. The deposition conditions were as follows: boat temperature 220-225 ° C, deposition rate 0.3-0.5 nm / s,
The substrate temperature was room temperature.
これを真空槽より取り出し、上記発光層の上にステン
レススチール製のマスクを設置し、再び基板ホルダーに
固定した。This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder.
次にモリブデン製の抵抗加熱ボートにマグネシウムリ
ボン1gを入れ、また異なるモリブデン製の抵抗加熱ボー
トにインジウム500mg装着した。Next, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of indium was mounted on a different molybdenum resistance heating boat.
その後真空槽を２×10-4Paまで減圧してから、インジ
ウムを0.03〜0.08nm/sの蒸着速度で、同時にもう一方の
ボートよりマグネシウムを1.7〜2.8nm/sの蒸着速度で蒸
着し始めた。Then, the pressure in the vacuum chamber was reduced to 2 × 10 -4 Pa, and then indium was deposited at a deposition rate of 0.03 to 0.08 nm / s and, simultaneously, magnesium was deposited from the other boat at a deposition rate of 1.7 to 2.8 nm / s. Was.
ボートの温度はインジウム，マグネシウムそれぞれ80
0℃,500℃程度であった。上記条件でマグネシウムとイ
ンジウムの混合金属電極を発光層の上に150nm積層蒸着
し、対向電極とした。Boat temperature is 80 for indium and magnesium for each
It was about 0 ° C and 500 ° C. Under the above conditions, a mixed metal electrode of magnesium and indium was deposited in a thickness of 150 nm on the light emitting layer to form a counter electrode.
この素子にそれぞれITO電極を陽極，マグネシウム：
インジウム電極を陰極として直流15Vを印加すると、電
流が100mA/cm2程度流れ、青色発光を得た。ピーク波長
は分光測定より482nmであった。発光輝度は250cd/m2で
あり、明所で充分光っているのが確認できた。This element has an ITO electrode as anode and magnesium:
When a direct current of 15 V was applied using the indium electrode as a cathode, a current of about 100 mA / cm 2 flowed, and blue light emission was obtained. The peak wavelength was 482 nm from the spectroscopic measurement. The light emission luminance was 250 cd / m 2 , and it was confirmed that the light was sufficiently lit in a light place.
以上により青色のEL励起光源が作製できた。 Thus, a blue EL excitation light source was manufactured.
（２）波長変換蛍光材料部の製造 まず上記の構造のクマリン153を4mgとポリメチルメタ
クリレート（PMMA）1.2gをジクロロメタン11gに溶解
し、クマリン153が分散されたPMMAのジクロロメタン溶
液を作製した。クマリンの分散濃度は対PMMA比1.3×10
-2モル／であった。(2) Production of wavelength conversion fluorescent material First, 4 mg of coumarin 153 having the above structure and 1.2 g of polymethyl methacrylate (PMMA) were dissolved in 11 g of dichloromethane to prepare a dichloromethane solution of PMMA in which coumarin 153 was dispersed. Coumarin dispersion concentration is 1.3 × 10 compared to PMMA
-2 mol /.
次によく洗浄された25mm×75mm×1.1mmの大きさのガ
ラス基板上にこの溶液を5ml滴下し、前面に展開した。
これを大気中に一昼夜放置し自然乾燥した。Next, 5 ml of this solution was dropped on a well-washed glass substrate of 25 mm × 75 mm × 1.1 mm and spread on the front surface.
This was left in the air for 24 hours to dry naturally.
その後真空乾燥機で真空度0.1Torr,温度50℃の条件で
２時間乾燥し溶媒のジクロロメタンを完全に除去した。
その結果クマリン153が上記濃度分散された膜厚80μｍ
のPMMA薄膜ができた。Thereafter, the resultant was dried with a vacuum drier under the conditions of a degree of vacuum of 0.1 Torr and a temperature of 50 ° C. for 2 hours to completely remove dichloromethane as a solvent.
As a result, the coumarin 153 was dispersed in the above concentration to a thickness of 80 μm.
Of PMMA thin film
（３）EL素子の発光測定 （１）で作製したPESBを発光層とするEL素子は上述し
たように15V印加時、250cd/m2の青色発光を得た。発光
色は色度的にもCIE色度座標がｘ＝0.14,y＝0.20でBlue
であった。次に（２）で作製したクマリン153分散膜をE
L素子のITO透明電極側に置き重ねて、クマリン153分散
膜を通して同じく15V印加時の発光を観測した。緑色で2
00cd/m2の発光が観測された。発光色は色度的にもCIE色
度座標がｘ＝0.17,y＝0.43でGreenであった。(3) Luminescence measurement of EL element The EL element using PESB as the light emitting layer produced in (1) emitted blue light of 250 cd / m 2 when 15 V was applied as described above. The emission color is Blue with CIE chromaticity coordinates x = 0.14, y = 0.20 in terms of chromaticity.
Met. Next, the coumarin 153 dispersion film prepared in (2) was
The device was placed on the ITO transparent electrode side of the L element, and light emission was also observed when a voltage of 15 V was applied through a coumarin 153 dispersion film. 2 in green
Emission of 00 cd / m 2 was observed. The emission color was Green with CIE chromaticity coordinates of x = 0.17 and y = 0.43 also in terms of chromaticity.
このように波長変換蛍光材料であるクマリン分散膜を
青いEL光の前に置くことにより容易に緑色の変換光が得
られた。As described above, by placing the coumarin dispersion film as the wavelength conversion fluorescent material in front of the blue EL light, green converted light was easily obtained.
実施例２ （１）有機EL材料部の製造 実施例１と同様にして製造した。Example 2 (1) Production of Organic EL Material Part Production was performed in the same manner as in Example 1.
（２）波長変換蛍光材料部の製造 実施例１と同様の方法で上記の構造のDCM4mgとPMMA1.
2gをジクロロメタン11gに溶解し、DCMのPMMA分散膜を作
製した。DCMの分散濃度は対PMMA比1.3×10-2モル／で
あった。作製された分散膜の膜厚は80μｍであった。(2) Production of wavelength conversion fluorescent material In the same manner as in Example 1, 4 mg of DCM having the above structure and PMMA1.
2 g was dissolved in 11 g of dichloromethane to prepare a PMMA dispersion film of DCM. The dispersion concentration of DCM was 1.3 × 10 -2 mol / PMMA ratio. The thickness of the prepared dispersion film was 80 μm.
（３）EL素子の発光測定 （１）で作製したPESBを発光層とするEL素子では上述
の如く15V印加時、250cd/m2の発光を得た。発光色のCIE
色度座標もｘ＝0.14,y＝0.20で青色であった。(3) Measurement of light emission of EL element The EL element using PESB as the light emitting layer produced in (1) emitted light of 250 cd / m 2 when 15 V was applied as described above. Emission color CIE
The chromaticity coordinates were also blue with x = 0.14 and y = 0.20.
次に（２）で作製したDCM分散膜をEL素子のITO透明電
極側に置き重ねて、DCM分散膜を通して同じく15V印加時
の発光を観測すると黄緑色で輝度約12cd/m2が得られ
た。Then (2) the DCM dispersion film fabricated on top placed ITO transparent electrode side of the EL device, likewise luminance of about 12 cd / m 2 when observing the emission at 15V is applied in yellow-green is obtained through DCM dispersion film .
その時の発光色のスペクトルのCIE色度座標はｘ＝0.4
0,y＝0.58で色度的にはYellow Greenであった。このよ
うに波長変換蛍光材料であるDCM分散膜を青いEL光の前
に置くことにより容易に黄緑色の変換光が得られた。The CIE chromaticity coordinate of the emission color spectrum at that time is x = 0.4
At 0, y = 0.58, the chromaticity was Yellow Green. Thus, yellow-green converted light was easily obtained by placing the DCM-dispersed film as the wavelength conversion fluorescent material in front of the blue EL light.
実施例３ （１）有機EL材料部の製造 実施例１と同様にして製造した。Example 3 (1) Production of Organic EL Material Part The production was performed in the same manner as in Example 1.
（２）波長変換蛍光材料部の製造 実施例１と同様な方法で上記の構造のピリジン１を4m
gとPMMA1.2gをジクロロメタン11gに溶解し、ピリジン１
のPMMA分散膜を作製した。(2) Production of wavelength conversion fluorescent material In the same manner as in Example 1, pyridine 1 having the above structure was
g and 1.2 g of PMMA are dissolved in 11 g of dichloromethane, and pyridine 1
Was prepared.
ピリジン１の分散濃度は対PMMA比1.0×10-2モル／
であった。作製した分散膜の膜厚は80μｍであった。The dispersion concentration of pyridine 1 was 1.0 × 10 -2 mol / PMMA ratio.
Met. The thickness of the prepared dispersion film was 80 μm.
（３）EL素子の発光測定 （１）で作製したPESBを発光層とするEL素子では上述
したように15V印加時、250cd/m2の青色発光を得た。発
光色は色度的にもCIE色度座標がｘ＝0.15,y＝0.23でBlu
eであった。(3) Luminescence measurement of EL element The EL element using PESB as the light emitting layer produced in (1) emitted blue light of 250 cd / m 2 when 15 V was applied as described above. The emission color is CIE chromaticity coordinate x = 0.15, y = 0.23 and Blu in chromaticity.
e.
次に（２）で作製したピリジン１分散膜をEL素子のIT
O透明電極側に置き重ねて、ピリジン１分散膜を通して
同じく10V印加時の発光を観測すると白色で100cd/m2と
いう結果が得られた。Next, the pyridine 1 dispersion film prepared in (2) was used for the EL device IT
When it was placed on the O transparent electrode side and the light emission was also observed when a voltage of 10 V was applied through a pyridine 1 dispersed film, the result was 100 cd / m 2 in white.
その時の発光色のスペクトルのCIE色度座標はｘ＝0.2
7,y＝0.37で色度的にはWhiteであった。このようにある
種の色素の分散膜を用いると適当な膜厚、分散濃度を選
べばELの透過光と色素からの蛍光が混ざった完全な白色
の変換光が容易に得られることがわかった。The CIE chromaticity coordinate of the emission color spectrum at that time is x = 0.2
At 7, y = 0.37, the chromaticity was White. In this way, it was found that using a dispersion film of a certain kind of dye, if the appropriate film thickness and dispersion concentration were selected, it was possible to easily obtain a completely white converted light in which the transmitted light of EL and the fluorescence from the dye were mixed. .
実施例４ （１）有機EL材料部の製造 25mm×75mm×1.1mmのガラス基板上にITOを蒸着法にて
100nmの厚さで製膜したものを透明支持基板とした（HOY
A製）。この透明支持基板を市販の蒸着装置（日本真空
技術（株）製）の基板ホルダーに固定し、モリブデン製
の抵抗加熱ボートにN,N′−ジフェニル−N,N′−ビス−
（３−メチルフェニル）−〔1,1′ビフェニル〕−4,4′
−ジアミン（TPDA）を200mg入れ、また別のモリブデン
製ボートにｐ−クォーターフェニル（PQP）を200g入れ
て真空槽を１×10-4Paまで減圧した。Example 4 (1) Production of Organic EL Material Section ITO on a 25 mm x 75 mm x 1.1 mm glass substrate by vapor deposition
A film formed to a thickness of 100 nm was used as a transparent support substrate (HOY
A). This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N'-diphenyl-N, N'-bis- was added to a molybdenum resistance heating boat.
(3-methylphenyl)-[1,1'biphenyl] -4,4 '
200 mg of diamine (TPDA) and 200 g of p-quarterphenyl (PQP) were placed in another molybdenum boat, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa.
その後TPDA入りの前記ボートを215〜220℃まで加熱
し、TPDAを蒸着速度0.1〜0.3nm/sで透明支持基板上に蒸
着して、膜厚80nmの正孔注入層を製膜させた。Thereafter, the boat containing TPDA was heated to 215 to 220 ° C., and TPDA was deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s to form a hole injection layer having a thickness of 80 nm.
この時の基板温度は室温であった。これを真空槽より
取り出すことなく、正孔注入層の上に、もう一つのボー
トよりPQPを発光層として80nm積層蒸着した。蒸着条件
はボート温度が218℃で蒸着速度は0.3〜0.5nm/s,基板温
度は室温であった。The substrate temperature at this time was room temperature. Without taking this out from the vacuum chamber, PQP was deposited as a light emitting layer on the hole injecting layer by another boat to a thickness of 80 nm. The deposition conditions were as follows: boat temperature was 218 ° C, deposition rate was 0.3-0.5 nm / s, and substrate temperature was room temperature.
これを真空槽より取り出し、上記発光層の上にステン
レススチール製のマスクを設置し、再び基板ホルダーに
固定した。This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder.
次にモリブデン製の抵抗加熱ボートにマグネシウムリ
ボン1gを入れ、また別のモリブデン製の抵抗加熱ボート
にインジウム500mg装着した。Next, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of indium was mounted on another molybdenum resistance heating boat.
その後真空槽を２×10-4Paまで減圧してから、インジ
ウムを0.03〜0.08nm/sの蒸着速度で、同時にもう一方の
ボートよりマグネシウムを1.7〜2.8nm/sの蒸着速度で蒸
着し始めた。Then, the pressure in the vacuum chamber was reduced to 2 × 10 -4 Pa, and then indium was deposited at a deposition rate of 0.03 to 0.08 nm / s and, simultaneously, magnesium was deposited from the other boat at a deposition rate of 1.7 to 2.8 nm / s. Was.
ボートの温度はインジウム，マグネシウムそれぞれ80
0℃,500℃程度であった。上記条件でマグネシウムとイ
ンジウムの混合金属電極を発光層の上に150nm積層蒸着
し対向電極とした。Boat temperature is 80 for indium and magnesium for each
It was about 0 ° C and 500 ° C. Under the above conditions, a mixed metal electrode of magnesium and indium was deposited in a thickness of 150 nm on the light emitting layer to form a counter electrode.
この素子11個にそれぞれITO電極を陽極，マグネシウ
ム：インジウム電極を陰極として直流20Vを印加すると
どれも電流が25mA/cm2程度流れ、近紫外域から可視光青
色に及ぶ発光を得た。ピーク波長は分光測定より420nm
であった。発光強度はフォトダイオートの出力より0.2m
W/cm2程度であった。以上により近紫外域を発光するEL
励起光源が作製できた。When a direct current of 20 V was applied to each of the 11 devices using an ITO electrode as an anode and a magnesium: indium electrode as a cathode, a current of about 25 mA / cm 2 flowed, and emitted light ranging from near ultraviolet to visible light blue. The peak wavelength is 420 nm from the spectroscopic measurement
Met. The emission intensity is 0.2m from the output of the photo die auto.
It was about W / cm 2 . EL emitting near-ultraviolet light
An excitation light source could be made.
（２）波長変換蛍光材料部の製造 実施例１と同様樹脂分散型で作製した。用いた色素は
1,4−ビス（２−メチルスチリル）ベンゼン（OMSB）を
用い、OMSB4mgとPMMA1.2gを11gのジクロロメタンに溶解
し、OMSBのPMMA分散膜を作製した。(2) Production of Wavelength Conversion Fluorescent Material Section A resin dispersion type was produced in the same manner as in Example 1. The dye used was
Using 1,4-bis (2-methylstyryl) benzene (OMSB), 4 mg of OMSB and 1.2 g of PMMA were dissolved in 11 g of dichloromethane to prepare a PMMA-dispersed film of OMSB.
OMSB分散濃度はPMMAに対して比1.3×10-3モル／で
あった。その結果できた分散膜は50μｍであった。The OMSB dispersion concentration was 1.3 × 10 −3 mol / per PMMA. The resulting dispersion film was 50 μm.
（３）EL素子の発光測定 （１）で作製したPQPを発光層とするEL素子は上述し
たように近紫外光を発光する（可視光でも発光）励起光
源となっている。(3) Luminescence measurement of EL element The EL element using PQP as the light emitting layer prepared in (1) is an excitation light source that emits near-ultraviolet light (also emits visible light) as described above.
発光色は色度的にはCIE色度座標がｘ＝0.16,y＝0.06
でPurplish Blueであった。次に（２）で作製したOMSB
分散膜をEL素子のITP透明電極側に置き重ねて、OMSB分
散膜を通して20V印加時、青で明所可視の発光が得られ
た。その時の発光色はCIE色度座標がｘ＝0.14,y＝0.19
となり色度的にも青色であった。The emission color is chromatically CIE chromaticity coordinate x = 0.16, y = 0.06
Was Purplish Blue. Next, the OMSB prepared in (2)
The dispersion film was placed on the ITP transparent electrode side of the EL device, and when a voltage of 20 V was applied through the OMSB dispersion film, blue light-visible light was emitted. The emission color at that time is such that the CIE chromaticity coordinates are x = 0.14, y = 0.19
And the color was blue.
このように波長変換蛍光材料であるOMSB分散膜を近紫
外線を含むELの前に置くと、蛍光材料がELを吸収して青
色の蛍光を発し、結果的には容易に青色の変換光が得ら
れることがわかった。When the OMSB dispersion film, which is a wavelength conversion fluorescent material, is placed in front of the EL containing near-ultraviolet light, the fluorescent material absorbs the EL and emits blue fluorescence, and as a result, blue converted light is easily obtained. I knew it could be done.
実施例５ （１）有機EL材料部の製造 25mm×75mm×1.1mmのガラス基板上にITOを蒸着法にて
100nmの厚さで製膜したものを透明支持基板とした（HOY
A製）。この透明支持基板を市販の蒸着装置（日本真空
技術（株）製）の基板ホルダーに固定しモリブデン製の
抵抗加熱ボートにN,N′−ジフェニル−N,N′−ビス−
（３−メチルフェニル）−〔1,1′ビフェニル〕−4,4′
−ジアミン（TPDA）を200mg入れ、また別のモリブデン
製ボートに1,4−ビス（2,2−ジ−ｐ−トリルビニル）ベ
ンゼン（DTVB）を200mg入れて真空槽を１×10-4Paまで
減圧した。Example 5 (1) Production of organic EL material section ITO is deposited on a glass substrate of 25 mm x 75 mm x 1.1 mm by vapor deposition.
A film formed to a thickness of 100 nm was used as a transparent support substrate (HOY
A). This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and N, N'-diphenyl-N, N'-bis- was added to a molybdenum resistance heating boat.
(3-methylphenyl)-[1,1'biphenyl] -4,4 '
-200 mg of diamine (TPDA) and 200 mg of 1,4-bis (2,2-di-p-tolylvinyl) benzene (DTVB) in another molybdenum boat, and the vacuum chamber is filled to 1 × 10 -4 Pa The pressure was reduced.
その後TPDA入りの前記ボートを215〜220℃まで加熱
し、TPDAを蒸着速度0.1〜0.3nm/sで透明支持基板上に蒸
着して、膜厚60nmの正孔注入層を製膜させた。Thereafter, the boat containing TPDA was heated to 215 to 220 ° C., and TPDA was deposited on the transparent support substrate at a deposition rate of 0.1 to 0.3 nm / s to form a 60-nm-thick hole injection layer.
この時の基板温度は室温であった。これを真空槽より
取り出すことなく、正孔注入層の上に、もう一つのボー
トよりDTVBを発光層として80nm積層蒸着した。蒸着条件
はボート温度が237〜238℃で蒸着速度は0.1〜0.3nm/s,
基板温度は室温であった。The substrate temperature at this time was room temperature. Without taking this out of the vacuum chamber, DTVB was deposited on the hole injection layer by another boat as a light emitting layer with a thickness of 80 nm as a light emitting layer. The deposition conditions were as follows: boat temperature 237-238 ° C, deposition rate 0.1-0.3 nm / s,
The substrate temperature was room temperature.
これを真空槽より取り出し、上記発光層の上にステン
レススチール製のマスクを設置し、再び基板ホルダーに
固定した。This was taken out of the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed again to the substrate holder.
次にモリブデン製の抵抗加熱ボートにマグネシウムリ
ボン1gをいれ、また別のモリブデン製の抵抗加熱ボート
にインジウム500mg装着した。Next, 1 g of a magnesium ribbon was placed in a molybdenum resistance heating boat, and 500 mg of indium was mounted on another molybdenum resistance heating boat.
その後真空槽を２×10-4Paまで減圧してから、インジ
ウムを0.03〜0.08nm/sの蒸着速度で、同時にもう一方の
ボートよりマグネシウムを1.7〜2.8nm/sの蒸着速度で蒸
着し始めた。Then, the pressure in the vacuum chamber was reduced to 2 × 10 -4 Pa, and then indium was deposited at a deposition rate of 0.03 to 0.08 nm / s and, simultaneously, magnesium was deposited from the other boat at a deposition rate of 1.7 to 2.8 nm / s. Was.
ボートの温度はインジウム，マグネシウムそれぞれ80
0℃,500℃程度であった。上記条件でマグネシウムとイ
ンジウムの混合金属電極を発光層の上に150nm積層蒸着
し対向電極とした。Boat temperature is 80 for indium and magnesium for each
It was about 0 ° C and 500 ° C. Under the above conditions, a mixed metal electrode of magnesium and indium was deposited in a thickness of 150 nm on the light emitting layer to form a counter electrode.
この素子のITO電極を陽極，マグネシウム：インジウ
ム電極を陰極として直流15Vを印加すると、どれも電流
が28mA/cm2程度流れ、青色発光を得た。ピーク波長は分
光測定より486nmであった。発光輝度は210cd/cm2であ
り、明所で充分光っているのが確認できた。When a direct current of 15 V was applied using the ITO electrode of the element as an anode and the magnesium: indium electrode as a cathode, a current of about 28 mA / cm 2 flowed, and blue light emission was obtained. The peak wavelength was 486 nm from the spectroscopic measurement. The light emission luminance was 210 cd / cm 2 , and it was confirmed that the light was sufficiently lit in a light place.
以上により青色（色度的にはBlue Green）のEL励起光
源が作製できた。As described above, a blue (blue-green) EL excitation light source was produced.
（２）波長変換蛍光材料の製造 実施例３で作製したピリジン１のPMMA分散膜を５枚重
ねることにより、厚さ400μｍのピリジン1PMMA分散膜を
作製した。(2) Production of Wavelength-Converting Fluorescent Material By stacking five PMMA-dispersed films of pyridine 1 produced in Example 3, a pyridine-1 PMMA-dispersed film having a thickness of 400 μm was produced.
ピリジン１の分散濃度は、実施例３と同様に1.0×10
-2モル／とした。The dispersion concentration of pyridine 1 was 1.0 × 10
-2 mol /.
（３）EL素子の発光測定 （１）で作製したPTVBを発光層とするEL素子は上述し
たように15V印加時、210cd/m2の青色発光を得た。発光
色のCIE色度座標はｘ＝0.15,y＝0.28でBlue Greenであ
った。(3) Measurement of light emission of EL element The EL element using PTVB as the light emitting layer produced in (1) emitted blue light of 210 cd / m 2 when 15 V was applied as described above. The CIE chromaticity coordinates of the emission color were x = 0.15, y = 0.28 and Blue Green.
次に（２）で作製したピリジン１分散膜をEL素子のIT
O透明電極側に置き重ねて、ピリジン１分散膜を通して1
9.5V印加時の発光を測定した。得られる光は明所可視オ
レンジ色であった。Next, the pyridine 1 dispersion film prepared in (2) was used for the EL device IT
O Place it on the transparent electrode side
Light emission when 9.5 V was applied was measured. The resulting light was bright orange in the light.
この時のCIE座標はｘ＝0.54,y＝0.45でYellowish Ora
ngeであった。The CIE coordinates at this time are x = 0.54, y = 0.45 and Yellowish Ora
nge.
このように波長変換蛍光材料であるピリジン１分散膜
の膜厚を厚くすることでELの透過成分を抑えて、得られ
る発光を蛍光が支配的なオレンジ色にできた。As described above, by increasing the thickness of the pyridine 1 dispersion film, which is a wavelength conversion fluorescent material, the transmission component of EL was suppressed, and the obtained light emission was able to be orange in which fluorescence is dominant.
実施例６及び７ 実施例５（１）で作製した有機EL材料部のDTVBと実施
例１（２）で作製したクマリン153を用いて、発光測定
を行った（実施例６）。さらに実施例５（１）で作製し
た有機EL材料部のDTVBと実施例２（２）で作製したDCM
を用いて、発光測定を行った（実施例７）。測定要領は
実施例１と同様である。Examples 6 and 7 Luminescence was measured using the DTVB of the organic EL material part produced in Example 5 (1) and the coumarin 153 produced in Example 1 (2) (Example 6). Further, the DTVB of the organic EL material part manufactured in Example 5 (1) and the DCM manufactured in Example 2 (2)
Was used to measure luminescence (Example 7). The measuring procedure is the same as that of the first embodiment.
結果を以下の表に示す。 The results are shown in the table below.
表中にはCIE色度座標における発光色及び発光輝度を
示す。 The emission color and emission luminance at the CIE chromaticity coordinates are shown in the table.
波長変換前は、蛍光材料を置き重ねしない状態のELの
みの光であり、波長変換後は、蛍光材料を置き重ねた状
態の発光を示す。Before the wavelength conversion, the light is emitted only by the EL without the fluorescent material placed thereon, and after the wavelength conversion, the light emission shows the light with the fluorescent material placed thereon.
実施例8,9及び10 有機EL材料部の発光層として1,4ビス（４−メチルス
チリル）ベンゼン（PMSB）を用い、蛍光材料として実施
例１（２）で作製したクマリン153を用いた場合（実施
例８）、有機EL材料部の発光層として1,4ビス（４−メ
チルスチリル）ベンゼン（PMSB）を用い、蛍光材料とし
て実施例２（２）で作製したDCMを用いた場合（実施例
９）、有機EL材料部の発光層として1,4ビス（４−メチ
ルスチリル）ベンゼン（PMSB）を用い、蛍光材料として
実施例３（２）で作製したピリジン１を用いた場合（実
施例10）の発光測定をそれぞれ行った。Examples 8, 9, and 10 In the case where 1,4 bis (4-methylstyryl) benzene (PMSB) was used as the light emitting layer of the organic EL material portion, and the coumarin 153 prepared in Example 1 (2) was used as the fluorescent material. (Example 8) In the case where 1,4 bis (4-methylstyryl) benzene (PMSB) was used as the light emitting layer of the organic EL material part and the DCM prepared in Example 2 (2) was used as the fluorescent material (Example Example 9) In the case where 1,4 bis (4-methylstyryl) benzene (PMSB) is used as the light emitting layer of the organic EL material part and pyridine 1 prepared in Example 3 (2) is used as the fluorescent material (Example The luminescence measurement of 10) was performed respectively.
測定は実施例６と同じであり、有機EL材料部の作製の
方法は、実施例１（１）のPESBの場合と同様である。但
し、PMSBの場合ボート温度を230〜240℃に設定し蒸着を
行った。The measurement was the same as in Example 6, and the method for producing the organic EL material portion was the same as that for the PESB in Example 1 (1). However, in the case of PMSB, vapor deposition was performed with the boat temperature set at 230 to 240 ° C.
結果を以下の表に示す。 The results are shown in the table below.
実施例11,12及び13 有機EL材料部を発光層として、トランス−4,4′−ジ
フェニルスチルベン（DPS）を用い、蛍光材料として実
施例１（２）で作製したクマリン153を用いた場合（実
施例11）、有機EL材料部を発光層として、トランス−4,
4′−ジフェニルスチルベン（DPS）を用い、蛍光材料と
して実施例２（２）で作製したDCMを用いた場合（実施
例12）、有機EL材料部を発光層として、トランス−4,
4′−ジフェニルスチルベン（DPS）を用い、蛍光材料と
して実施例３（２）で作製したピリジン１を用いた場合
（実施例13）の発光測定をそれぞれ行った。 Examples 11, 12 and 13 Trans-4,4'-diphenylstilbene (DPS) was used as the light emitting layer in the organic EL material part, and coumarin 153 prepared in Example 1 (2) was used as the fluorescent material ( Example 11) Trans-4,
When 4'-diphenylstilbene (DPS) was used and the DCM prepared in Example 2 (2) was used as the fluorescent material (Example 12), the organic EL material part was used as the light emitting layer, and the trans-4,
Light emission was measured using 4'-diphenylstilbene (DPS) and pyridine 1 prepared in Example 3 (2) as a fluorescent material (Example 13).
測定要領は実施例６と同様であり、有機EL材料部の作
製は、ボート温度が205〜210℃であること以外は実施例
１（１）と同様であった。結果を次表に示す。The measurement procedure was the same as in Example 6, and the preparation of the organic EL material part was the same as Example 1 (1) except that the boat temperature was 205 to 210 ° C. The results are shown in the following table.
実施例14 （１）有機EL材料部の製造 実施例５と同様にして製造した。 Example 14 (1) Production of Organic EL Material Part Production was performed in the same manner as in Example 5.
（２）波長変換蛍光材料１の製造 実施例５と同様な方法でさらに厚いピリジン１のPMMA
分散膜を作製した。８枚重ねることにより、膜厚が600
μｍ程度のピリジン1,PMMA分散膜を作製した。(2) Production of wavelength conversion fluorescent material 1 PMMA of thicker pyridine 1 in the same manner as in Example 5
A dispersion film was prepared. By stacking eight sheets, the film thickness becomes 600
A pyridine 1, PMMA dispersion film of about μm was produced.
（３）波長変換蛍光材料２の製造 上記の構造のローダミン6G 6mgとPMMA1.2gを11gのジ
クロロメタンに溶解し、実施例１（２）と同様キャスト
法によりローダミン6GPMMA分散膜を作製した。ローダミ
ン6Gの分散濃度は1.2×10-2モル／とした。(3) Production of wavelength conversion fluorescent material 2 6 mg of rhodamine 6G having the above structure and 1.2 g of PMMA were dissolved in 11 g of dichloromethane, and a rhodamine 6GPMMA dispersion film was produced by the same casting method as in Example 1 (2). The dispersion concentration of rhodamine 6G was 1.2 × 10 -2 mol /.
できあがったPMMA分散膜の厚さは100μｍ程度であっ
た。The thickness of the completed PMMA dispersed film was about 100 μm.
これを２枚重ねることにより膜厚200μｍのローダミ
ン6G PMMA分散膜を作製した。By stacking two of them, a rhodamine 6G PMMA dispersion film having a thickness of 200 μm was produced.
（４）EL素子の製造 （１）で作製したDTVBを発光層とするEL素子は上述し
たように15V印加時、210cd/m2の青色発光を得た。発光
色のCIE色度座標はｘ＝0.15,y＝0.28でBlue Greenであ
った。(4) Production of EL Element The EL element using DTVB as the light emitting layer produced in (1) emitted blue light of 210 cd / m 2 when 15 V was applied as described above. The CIE chromaticity coordinates of the emission color were x = 0.15, y = 0.28 and Blue Green.
次に（２）で作製したピリジン１分散膜と（３）で作
製したローダミン6G分散膜をEL素子のITO透明電極側に
置き重ねて、これら二つの分散膜を通して15V印加時の
発光を観測した。明所可視赤色の発光であった。この時
のCIE座標はｘ＝0.62,y＝0.37で色度的にはReddish Ora
ngeであった。Next, the pyridine 1 dispersion film prepared in (2) and the rhodamine 6G dispersion film prepared in (3) were placed on the ITO transparent electrode side of the EL device, and light emission was observed when 15 V was applied through these two dispersion films. . Light was emitted in visible red. The CIE coordinates at this time are x = 0.62, y = 0.37 and the chromaticity is Reddish Ora
nge.
ピリジン１のみの場合と比較し、より赤色化した。 The color became more red as compared with the case of only pyridine 1.
以上のように蛍光材料は単一の有機色素ばかりでなく
複数個用いても、その組み合わせより変換光の選択性が
向上することがわかった。As described above, it was found that, even when a plurality of fluorescent materials were used in addition to a single organic dye, selectivity of converted light was improved by a combination thereof.
実施例15 （１）有機EL材料部の製造 実施例１と同様な方法により1,4ビス（２−フェニ
ル，−２−ｐ−トリルビニル）ベンゼン（PTVB）を発光
層、TPDAを正孔注入層とする積層型EL素子部が作製し
た。PTVB蒸着時のボート温度が200℃であった以外は実
施例１と同様に作製した。Example 15 (1) Production of Organic EL Material Section In the same manner as in Example 1, 1,4 bis (2-phenyl, -2-p-tolylvinyl) benzene (PTVB) was used as a light emitting layer, and TPDA was used as a hole injection layer. Was manufactured. It was produced in the same manner as in Example 1 except that the boat temperature during PTVB deposition was 200 ° C.
できあがったEL素子部の発光は青色でピーク波長が48
5nmであった。The resulting EL element emits blue light with a peak wavelength of 48.
It was 5 nm.
両電極間に20V印加すると90mA/cm2の電流が流れ、発
光輝度500cd/m2を得た。When a voltage of 20 V was applied between both electrodes, a current of 90 mA / cm 2 flowed, and a light emission luminance of 500 cd / m 2 was obtained.
（２）波長変換蛍光材料部の製造 上記の如き構造のフェノキサゾン９を4mgとPMMA1.2g
をジクロロメタン11gに溶解し、実施例１（２）と同様
キャスト法によりフェノキサゾン9PMMA分散膜を作製し
た。フェノキサゾン９の分散濃度は、1.3×10-2モル／
であった。(2) Production of wavelength conversion fluorescent material 4 mg of phenoxazone 9 having the above structure and 1.2 g of PMMA
Was dissolved in 11 g of dichloromethane, and a phenoxazone 9PMMA dispersed membrane was prepared by the same casting method as in Example 1 (2). The dispersion concentration of phenoxazone 9 was 1.3 × 10 -2 mol /
Met.
できあがったPMMA分散膜の厚さは、80μｍ程度であっ
た。The thickness of the completed PMMA dispersion film was about 80 μm.
これを３枚重ねることにより膜厚240μｍのフェノキ
サゾン9PMMA分散膜を作製した。By stacking three of them, a phenoxazone 9PMMA dispersion film having a thickness of 240 μm was prepared.
（３）EL素子の発光測定 （１）で作製したPTVBを発光層とするEL素子の発光色
はCIE色度座標はｘ＝0.15,y＝0.25で色度的にはGreenis
h Blueであった。(3) Emission measurement of EL element The emission color of the EL element using PTVB as the light emitting layer prepared in (1) is CIE chromaticity coordinate x = 0.15, y = 0.25, and chromaticity is Greenis
h Blue.
これに（２）で作製したフェノキサゾン分散膜と実施
例３の（２）の要領で作製したピリジン１のPMMA分散膜
（膜厚240μｍ）をITO透明電極に置き重ねて、これら二
つの分散膜を通して15V印加時の発光を観測した。明暗
所可視赤色の発光を得た。The phenoxazone-dispersed film prepared in (2) and the PMMA-dispersed film of pyridine 1 (240 μm in film thickness) prepared in the manner of (2) in Example 3 were placed on the ITO transparent electrode, and passed through these two dispersed films. Light emission at the time of 15V application was observed. Visible red light was emitted in bright and dark places.
この時のCIE色度座標はｘ＝0.60,y＝0.31で色度的に
赤であった。At this time, the CIE chromaticity coordinates were x = 0.60 and y = 0.31, and the chromaticity was red.
このようにフェノキサゾン，ピリジンという二つの蛍
光材料を用いることにより、色度的にGreenish Blueの
光がELではなかなか得にくい赤色に容易に変換すること
ができた。Thus, by using two fluorescent materials, phenoxazone and pyridine, it was possible to easily convert greenish blue light into red which is difficult to obtain with EL in terms of chromaticity.
実施例16 （１）有機EL材料部の製造 実施例15（１）と同様にして製造した。Example 16 (1) Production of Organic EL Material Part The organic EL material part was produced in the same manner as in Example 15 (1).
（２）波長変換蛍光材料部の製造 実施例15（２）と同様にして製造した。(2) Manufacture of wavelength conversion fluorescent material The same was manufactured in the same manner as in Example 15 (2).
（３）EL素子の発光測定 （１）で作製したPTVBを発光層とするEL素子の発光色
はCIE色度座標はｘ＝0.15,y＝0.25で色度的にはGreenis
h Blueであった。(3) Emission measurement of EL element The emission color of the EL element using PTVB as the light emitting layer prepared in (1) is CIE chromaticity coordinate x = 0.15, y = 0.25, and chromaticity is Greenis
h Blue.
これに（２）で作製したフェノキサゾン分散膜とさら
にカラーフィルターY52（HOYA製）をITO透明電極に置き
重ねて、これらを通して15V印加時の発光を観測した。
明暗所可視赤色の発光を得た。The phenoxazone-dispersed film prepared in (2) and the color filter Y52 (manufactured by HOYA) were further placed on the ITO transparent electrode, and the light emission when 15 V was applied was observed through these.
Visible red light was emitted in bright and dark places.
この時のCIE色度座標はｘ＝0.62,y＝0.33で色度的に
赤であった。At this time, the CIE chromaticity coordinates were x = 0.62, y = 0.33, and the chromaticity was red.
このようにフェノキサゾン蛍光材料とカラーフィルタ
ーの組合せにより、色度的にGreenish Blueの光がELで
はなかなか得にくい赤色光に容易に変換することができ
た。As described above, the combination of the phenoxazone fluorescent material and the color filter made it possible to easily convert greenish blue light into red light, which is difficult to obtain with EL.
以上のように、本発明のEL素子は変換光の波長範囲が
広く、有機EL素子と蛍光材料の組み合せにより、青，
緑，赤の三原色が表現可能である。したがって、フルカ
ラー表示が可能である。As described above, the EL device of the present invention has a wide wavelength range of the converted light, and the combination of the organic EL device and the fluorescent material allows blue,
The three primary colors of green and red can be expressed. Therefore, full color display is possible.
さらに蛍光材料部の膜厚、蛍光材料の分散濃度等を変
化させることによりEL透過光と蛍光が混合され、白色の
表現も可能であり、白色発光素子としても利用できる。Further, by changing the thickness of the fluorescent material portion, the dispersion concentration of the fluorescent material, and the like, the EL transmitted light and the fluorescent light are mixed, and a white color can be expressed, and the device can be used as a white light emitting element.
また、EL素子の蛍光材料部を着脱可能な積層型とする
ことができ、蛍光材料部を変換することにより発光波長
を容易に変化させる事が可能である。Further, the fluorescent material portion of the EL element can be a detachable laminated type, and the emission wavelength can be easily changed by changing the fluorescent material portion.
したがって、本発明のEL素子は種々の表示材料として
幅広く利用することができる。Therefore, the EL device of the present invention can be widely used as various display materials.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−264692（ＪＰ，Ａ) 特開 平２−158091（ＪＰ，Ａ) 実開 昭63−111795（ＪＰ，Ｕ) 実開 昭63−121396（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.6，ＤＢ名) H05B 33/00 - 33/28──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-264692 (JP, A) JP-A-2-158091 (JP, A) Full-scale open 63-111795 (JP, U) 121396 (JP, U) (58) Fields surveyed (Int. Cl. 6 , DB name) H05B 33/00-33/28
Claims (3)
エレクトロルミネッセンス材料部が、直流電圧あるいは
パルス電圧を印加して青色発光あるいは青緑色発光させ
る有機化合物を含む発光材料からなる発光層を有すると
共に、該有機エレクトロルミネッセンス材料部の両電極
間内部以外の位置に、前記発光層の発光を吸収し青緑色
から赤色までの少なくとも一つの色の可視光の蛍光を発
光する少なくとも一つの蛍光材料部を配設してなるエレ
クトロルミネッセンス素子。An organic electroluminescent material portion having a light emitting layer sandwiched between an anode and a cathode is made of a light emitting material containing an organic compound which emits blue light or blue green light by applying a DC voltage or a pulse voltage. And at least one fluorescent light that absorbs light emitted from the light emitting layer and emits visible light fluorescent light of at least one color from blue green to red at a position other than between the two electrodes of the organic electroluminescent material portion. An electroluminescent element in which a material section is provided.
成が、陽極／正孔注入輸送層／発光層／陰極あるいは陽
極／正孔注入輸送層／発光層／電子注入輸送層／陰極で
ある請求項１のエレクトロルミネッセンス素子。2. The composition of the organic electroluminescent material part is: anode / hole injection / transport layer / light emitting layer / cathode or anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode. Electroluminescence element.
項１又は２のエレクトロルミネッセンス素子。3. The electroluminescent device according to claim 1, wherein the fluorescent material portion comprises a plurality of fluorescent materials.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1289907A JP2795932B2 (en) | 1989-11-09 | 1989-11-09 | Electroluminescence element |
| US07/488,702 US5126214A (en) | 1989-03-15 | 1990-03-05 | Electroluminescent element |
| DE69025348T DE69025348T2 (en) | 1989-03-15 | 1990-03-09 | Electroluminescent element |
| EP90104505A EP0387715B1 (en) | 1989-03-15 | 1990-03-09 | Electroluminescent element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1289907A JP2795932B2 (en) | 1989-11-09 | 1989-11-09 | Electroluminescence element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03152897A JPH03152897A (en) | 1991-06-28 |
| JP2795932B2 true JP2795932B2 (en) | 1998-09-10 |
Family
ID=17749314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1289907A Expired - Lifetime JP2795932B2 (en) | 1989-03-15 | 1989-11-09 | Electroluminescence element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2795932B2 (en) |
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| JPH01254791A (en) * | 1988-04-02 | 1989-10-11 | Idemitsu Kosan Co Ltd | Thin-film electroluminescent element |
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