JP2017045650A - White light-emitting organic el element and white light-emitting organic el panel including the same - Google Patents
White light-emitting organic el element and white light-emitting organic el panel including the same Download PDFInfo
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- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- -1 amine compounds Chemical class 0.000 description 3
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 2
- BIXGISJFDUHZEB-UHFFFAOYSA-N 2-[9,9-bis(4-methylphenyl)fluoren-2-yl]-9,9-bis(4-methylphenyl)fluorene Chemical compound C1=CC(C)=CC=C1C1(C=2C=CC(C)=CC=2)C2=CC(C=3C=C4C(C5=CC=CC=C5C4=CC=3)(C=3C=CC(C)=CC=3)C=3C=CC(C)=CC=3)=CC=C2C2=CC=CC=C21 BIXGISJFDUHZEB-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- OSQXTXTYKAEHQV-WXUKJITCSA-N 4-methyl-n-[4-[(e)-2-[4-[4-[(e)-2-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]ethenyl]phenyl]phenyl]ethenyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(\C=C\C=2C=CC(=CC=2)C=2C=CC(\C=C\C=3C=CC(=CC=3)N(C=3C=CC(C)=CC=3)C=3C=CC(C)=CC=3)=CC=2)=CC=1)C1=CC=C(C)C=C1 OSQXTXTYKAEHQV-WXUKJITCSA-N 0.000 description 1
- LTUJKAYZIMMJEP-UHFFFAOYSA-N 9-[4-(4-carbazol-9-yl-2-methylphenyl)-3-methylphenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C(=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C)C(C)=C1 LTUJKAYZIMMJEP-UHFFFAOYSA-N 0.000 description 1
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
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- 150000002503 iridium Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- CECAIMUJVYQLKA-UHFFFAOYSA-N iridium 1-phenylisoquinoline Chemical compound [Ir].C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 CECAIMUJVYQLKA-UHFFFAOYSA-N 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
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- 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
- 230000000704 physical effect Effects 0.000 description 1
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- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 125000005504 styryl group Chemical group 0.000 description 1
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- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical class N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-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
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、有機ＥＬ素子に関し、特に、複雑な材料積層構成を排除することで工程を簡略化可能であり、かつ、高演色性の白色発光可能な白色発光有機ＥＬ素子に関するものである。 The present invention relates to an organic EL element, and more particularly to a white light-emitting organic EL element capable of simplifying the process by eliminating a complicated material laminated structure and capable of emitting white light with high color rendering.
白色発光有機ＥＬパネルにおいて、高効率な性能を持つパネルの作製のためには、複雑な材料積層構成により作製することが必要となってきている。複雑な材料積層構成になるに従い、それぞれの積層箇所に応じた機能を持つ材料が必要となり、材料種の増加や製造設備の肥大化から、製造コストの増加や生産性の低下が懸念される。例えば、特許文献１に記載の白色発光有機ＥＬパネルでは、２段積層型マルチユニット構造により形成されており、高効率が期待できる反面、各ユニット内に複数層の機能性材料の積層が必要となり、パネル作製工程の複雑化による生産性の低下を招き兼ねない。 In order to fabricate a white light-emitting organic EL panel having a highly efficient performance, it has become necessary to fabricate it with a complicated material laminated structure. As a complex material lamination structure is formed, a material having a function corresponding to each lamination position is required, and there is a concern about an increase in manufacturing cost and a decrease in productivity due to an increase in material types and enlargement of manufacturing equipment. For example, the white light-emitting organic EL panel described in Patent Document 1 is formed by a two-stage stacked multi-unit structure, and high efficiency can be expected. However, it is necessary to stack a plurality of functional materials in each unit. This can lead to a decrease in productivity due to the complexity of the panel manufacturing process.
このような課題に対して、本発明では、積層材料の種類を減らし、かつ、それぞれの積層箇所に応じた機能を満たすように、また、適正物性を有する無限の材料候補につき、必要機能を発揮するよう無限の組み合わせを実験的に最適化するのではなく、新たな発想により、低コストであり、より簡素化した工程にて高効率な性能を示し、さらに、高演色性で白色に近い色温度を持つ白色発光有機ＥＬ素子、及びこれを含むパネルを提供することを課題とする。 In response to such problems, the present invention demonstrates the necessary functions for an infinite number of material candidates having appropriate physical properties so as to reduce the types of laminated materials and satisfy the functions according to the respective laminated locations. Rather than experimentally optimizing infinite combinations, new ideas provide low-cost, high-efficiency performance with a simpler process, and color rendering that is close to white It is an object to provide a white light-emitting organic EL element having a temperature and a panel including the same.
このような課題に鑑み、本発明者らは検討の結果、同系統の機能を担う層は同一の材料を使用することで、使用する材料の種類を減らし、積層する箇所に応じた機能を発揮するように、基本的に層厚みを、場合によっては共蒸着組成を組み合わせて変更することにより、各機能の役割を十分に発揮しうることを見出し、本発明を完成させた。このような新たな発想、即ち、層厚みにより必要機能を発揮せしめる本発明の発想により、高性能有機ＥＬ素子、及びこれを含む有機ＥＬパネルを、低コスト、かつ、より簡易に作製することができるようになった。 In view of such problems, the present inventors have studied, and the layers responsible for the functions of the same system use the same material, thereby reducing the types of materials to be used and exhibiting functions according to the location to be laminated. Thus, the present inventors have found that the role of each function can be sufficiently exhibited by changing the layer thickness in combination with the co-deposition composition in some cases. With such a new idea, that is, the idea of the present invention in which a necessary function is exhibited by the layer thickness, a high-performance organic EL element and an organic EL panel including the same can be manufactured at low cost and more easily. I can do it now.
即ち、本発明は、透光性絶縁基板上に順に形成された、透光性陽極層、陽極側青発光ユニット、接続層、陰極側赤緑発光ユニット、及び反射性陰極層からなる白色発光有機ＥＬ素子であって、
該陽極側青発光ユニット、及び該陰極側赤緑発光ユニットの各々が、該透光性陽極層側から正孔注入層、正孔輸送層、発光層、電子輸送層、及び電子注入層を含み、
両ユニットの、
正孔注入層が、同一の、正孔輸送材料、及び電子受容性材料からなり、かつ、陰極側赤緑発光ユニット正孔注入層厚みが、陽極側青発光ユニット正孔注入層厚みの１．２倍以上、２倍以下であり、
正孔輸送層が、同一の正孔輸送材料からなり、かつ、陽極側青発光ユニット正孔輸送層厚みが、陰極側赤緑発光ユニット正孔輸送層厚みの２倍以上、４倍以下であり、
電子輸送層が、同一の電子輸送材料からなり、かつ、陽極側青発光ユニット電子輸送層厚みが、陰極側赤緑発光ユニット電子輸送層厚みの２倍以上、４倍以下であり、さらに、
電子注入層が、同一の、電子輸送材料、及び電子供与性材料からなり、かつ、陽極側青発光ユニット電子注入層厚みが、陰極側赤緑発光ユニット電子注入層厚みの１．２倍以上、２倍以下である、白色発光有機ＥＬ素子に関する。
That is, the present invention provides a white light-emitting organic layer comprising a light-transmitting anode layer, an anode-side blue light-emitting unit, a connection layer, a cathode-side red-green light-emitting unit, and a reflective cathode layer, which are sequentially formed on a light-transmitting insulating substrate. An EL element,
Each of the anode-side blue light-emitting unit and the cathode-side red-green light-emitting unit includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer from the translucent anode layer side. ,
Of both units,
1. The hole injection layer is made of the same hole transport material and electron accepting material, and the cathode side red / green light emitting unit hole injection layer thickness is 1. 2 times or more, 2 times or less,
The hole transport layer is made of the same hole transport material, and the anode side blue light emitting unit hole transport layer thickness is 2 to 4 times the cathode side red green light emitting unit hole transport layer thickness. ,
The electron transport layer is made of the same electron transport material, and the anode-side blue light-emitting unit electron transport layer thickness is 2 to 4 times the cathode-side red / green light-emitting unit electron transport layer thickness;
The electron injection layer is made of the same electron transport material and electron donating material, and the anode side blue light emitting unit electron injection layer thickness is 1.2 times or more of the cathode side red green light emitting unit electron injection layer thickness, The present invention relates to a white light-emitting organic EL device that is twice or less.
具体的には、陽極側青発光ユニット、及び陰極側赤緑発光ユニットを含む、安価かつ高性能の素子とする観点から好ましくは発光ユニットとしてこれら２つのユニットのみを含む２段積層の、白色有機ＥＬ積層構成において、正孔注入層、正孔輸送層、電子注入層、及び電子輸送層の夫々の材料が、１段目の陽極側青発光ユニットと、２段目の陰極側赤緑発光ユニットとで、同一の材料を用いて形成されており、正孔注入層は接続層に接する２段目の膜厚が厚く、電子注入層は接続層に接する１段目の膜厚が厚く、正孔輸送層は透光性陽極層側の１段目の膜厚は２段目の膜厚より厚く、電子輸送層は反射性陰極層側の２段目より１段目の膜厚の方が厚い構成となっている白色発光有機ＥＬ素子である。 Specifically, from the viewpoint of providing an inexpensive and high-performance element including an anode-side blue light-emitting unit and a cathode-side red-green light-emitting unit, a two-layered white organic layer including only these two units as a light-emitting unit is preferable. In the EL laminated structure, each material of the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer is composed of a first-stage anode-side blue light-emitting unit and a second-stage cathode-side red-green light-emitting unit. And the hole injection layer is thick at the second stage in contact with the connection layer, and the electron injection layer is thick at the first stage in contact with the connection layer. In the hole transport layer, the first layer on the translucent anode layer side is thicker than the second layer, and in the electron transport layer, the first layer is thicker than the second layer on the reflective cathode layer side. This is a white light-emitting organic EL element having a thick structure.
このような本発明の白色発光有機ＥＬ素子は、積層材料の種類が少ないので低コストであり、より簡素化した工程で製造できるにも拘わらず、高演色性で白色に近い色温度を持つ白色発光が可能であり、更に、以下の理由で高効率である。第一に、正孔注入層は接続層に接する２段目の膜厚がより厚いので接続層からの正孔供給が促進され、第二に、電子注入層は接続層に接する１段目の膜厚がより厚いので接続層からの電子供給が促進され、第三に、正孔輸送層は透光性陽極層側の１段目の膜厚がより厚いので正孔の過剰な供給を抑制し発光層内でのエキシトン生成が促され、第四に、電子輸送層は反射性陰極層側の２段目より１段目の膜厚の方が厚いので電子の過剰な供給を抑制し発光層内でのエキシトン生成が促される。このような１段目の陽極側青発光ユニットの発光性能をより高めるようにバランスさせた白色発光有機ＥＬ素子は、高効率であり、また、より白みを帯びた白色発光させることが比較的容易であり、より高い色温度を示す特性を得ることもできる。 Such a white light-emitting organic EL device of the present invention is low in cost because there are few kinds of laminated materials, and has a high color rendering property and a color temperature close to white, although it can be manufactured by a more simplified process. It can emit light and is highly efficient for the following reasons. First, since the hole injection layer is thicker in the second stage in contact with the connection layer, hole supply from the connection layer is promoted. Second, the electron injection layer is in the first stage in contact with the connection layer. The thicker film promotes electron supply from the connection layer, and third, the hole transport layer is thicker on the first stage on the translucent anode layer side, so it prevents excessive supply of holes. Exciton generation in the light emitting layer is promoted. Fourth, the electron transport layer is thicker in the first layer than the second layer on the reflective cathode layer side, so that excessive electron supply is suppressed and light emission is achieved. Exciton production in the layer is promoted. The white light-emitting organic EL element balanced so as to enhance the light-emitting performance of the first-stage anode-side blue light-emitting unit is highly efficient, and it is relatively easy to emit whiter white light. It is easy to obtain a characteristic exhibiting a higher color temperature.
また、前記陰極側赤緑発光ユニットは、赤色燐光材料、緑色燐光材料、及びホスト材料を含む赤緑燐光発光層を含む陰極側燐光赤緑発光ユニットとすることが好ましく、より高性能の素子となる。 The cathode-side red-green light emitting unit is preferably a cathode-side phosphorescent red-green light-emitting unit including a red-green phosphorescent light-emitting layer including a red phosphorescent material, a green phosphorescent material, and a host material. Become.
さらに、本発明は、本発明の白色発光有機ＥＬ素子を含む白色発光有機ＥＬパネルであって、
演色性のＲａ値、及びＲ９値が共に９０以上の白色光を発光し、かつ、
前記赤色燐光材料と、前記緑色燐光材料との最大発光ピーク波長が、６０ｎｍ以上離れている、白色発光有機ＥＬパネルに関する。
Furthermore, the present invention is a white light emitting organic EL panel comprising the white light emitting organic EL element of the present invention,
Emits white light with a Ra value of color rendering properties and an R 9 value of 90 or more, and
The present invention relates to a white light-emitting organic EL panel in which the maximum emission peak wavelength of the red phosphor material and the green phosphor material is 60 nm or more apart.
このような本発明の白色発光有機ＥＬパネルは、高効率素子を含むパネルであるにも拘わらず、低コストであり、より簡素化した工程で製造可能であり、さらに、高演色性の白色発光が可能である。 Such a white light-emitting organic EL panel of the present invention is a panel including a high-efficiency element, is low-cost, can be manufactured by a simplified process, and has a high color rendering white light emission. Is possible.
また、色温度が３８００Ｋ以上の白色光を発光する、白色発光有機ＥＬパネルとすることが好ましく、より白みを帯びた白色発光をするパネルとなる。 Moreover, it is preferable to set it as the white light emission organic electroluminescent panel which light-emits white light whose color temperature is 3800K or more, and becomes a panel which emits whiter white light.
本構成の白色発光有機ＥＬ素子は、低コストであり、より簡素化した工程にて高効率な性能を示し、白色に近い色温度を持つ白色発光を示すことができる。 The white light-emitting organic EL device having this configuration is low in cost, exhibits high efficiency in a more simplified process, and can emit white light having a color temperature close to white.
以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
（白色発光有機ＥＬ素子１）
本発明の白色発光有機ＥＬ素子１は、図１に示すように、透光性絶縁基板２上に形成されてなる透光性陽極層３と、反射性陰極層４とを備え、これら透光性陽極層３と反射性陰極層４とに挟持されてなる、透光性陽極層３側の陽極側青発光ユニット５と、反射性陰極層４側の陰極側赤緑発光ユニット７とをさらに備え、これら陽極側青発光ユニット５、及び陰極側赤緑発光ユニット７の間には、これらのユニットと接する接続層６が配置されている。
(White light emitting organic EL device 1)
As shown in FIG. 1, the white light-emitting organic EL device 1 of the present invention includes a light-transmitting anode layer 3 formed on a light-transmitting insulating substrate 2 and a reflective cathode layer 4. An anode-side blue light-emitting unit 5 on the light-transmitting anode layer 3 side and a cathode-side red-green light-emitting unit 7 on the reflective cathode layer 4 side, which are sandwiched between the conductive anode layer 3 and the reflective cathode layer 4 In addition, a connection layer 6 in contact with these units is disposed between the anode-side blue light-emitting unit 5 and the cathode-side red-green light-emitting unit 7.
また、本発明の白色発光有機ＥＬ素子１は、前記陽極側青発光ユニット５、及び前記陰極側赤緑発光ユニット７の各々が、前記透光性陽極層側３から、正孔注入層５１、７１、正孔輸送層５２、７２、発光層５３、７３、電子輸送層５４，７４、及び電子注入層５５、７５を含み、かつ、これら両ユニットの互いに対応する正孔注入層５１、及び７１と、正孔輸送層５２、及び７２と、電子輸送層５４，及び７４と、電子注入層５５、及び７５とは、同一の材料からなり、さらに、前記対応する層同士の厚みが一定の関係を満たすことを特徴とする。 Further, in the white light-emitting organic EL device 1 of the present invention, each of the anode-side blue light-emitting unit 5 and the cathode-side red-green light-emitting unit 7 includes a hole injection layer 51, a light-transmitting anode layer side 3, 71, hole transport layers 52 and 72, light emitting layers 53 and 73, electron transport layers 54 and 74, and electron injection layers 55 and 75, and hole injection layers 51 and 71 corresponding to each other in both units. The hole transport layers 52 and 72, the electron transport layers 54 and 74, and the electron injection layers 55 and 75 are made of the same material, and the thicknesses of the corresponding layers are constant. It is characterized by satisfying.
即ち、両ユニットの
正孔注入層５１、７１が、同一の、正孔輸送材料、及び電子受容性材料からなり、陰極側赤緑発光ユニット正孔注入層７１厚みが、陽極側青発光ユニット正孔注入層５１厚みの１．２倍以上、２倍以下であり、
正孔輸送層５２、７２が、同一の正孔輸送材料からなり、陽極側青発光ユニット正孔輸送層５２厚みが、陰極側赤緑発光ユニット正孔輸送層７２厚みの２倍以上、４倍以下であり、
電子輸送層５４，７４が、同一の電子輸送材料からなり、陽極側青発光ユニット電子輸送層５４厚みが、陰極側赤緑発光ユニット電子輸送層７４厚みの２倍以上、４倍以下であり、
電子注入層５５，７５が、同一の、電子輸送材料、及び電子供与性材料からなり、陽極側青発光ユニット電子注入層５５厚みが、陰極側赤緑発光ユニット電子注入層７５厚みの１．２倍以上、２倍以下である。
That is, the hole injection layers 51 and 71 of both units are made of the same hole transport material and electron accepting material, and the cathode side red / green light emitting unit hole injection layer 71 thickness is positive for the anode side blue light emitting unit positive. 1.2 times or more and 2 times or less of the thickness of the hole injection layer 51,
The hole transport layers 52 and 72 are made of the same hole transport material, and the thickness of the anode-side blue light-emitting unit hole transport layer 52 is more than twice the thickness of the cathode-side red-green light-emitting unit hole transport layer 72 by 4 times. And
The electron transport layers 54 and 74 are made of the same electron transport material, and the anode-side blue light-emitting unit electron transport layer 54 thickness is 2 to 4 times the cathode-side red / green light-emitting unit electron transport layer 74 thickness,
The electron injection layers 55 and 75 are made of the same electron transport material and electron donating material, and the anode side blue light emitting unit electron injection layer 55 thickness is 1.2 times the cathode side red green light emitting unit electron injection layer 75 thickness. It is 2 times or more.
言い換えると、本発明では、正孔注入層、正孔輸送層、電子注入層、電子輸送層のそれぞれの材料が、陽極側青発光ユニット５と陰極側赤緑発光ユニット７で同一の材料であり、正孔注入層は接続層６に接する陰極側赤緑発光ユニット７の膜厚が厚く、電子注入層は接続層６に接する陽極側青発光ユニット５の膜厚が厚く、また、正孔輸送層は、陽極側青発光ユニット５の膜厚が陰極側赤緑発光ユニット７の膜厚より厚く、電子輸送層は、陰極側赤緑発光ユニット７の膜厚より陽極側青発光ユニット５の膜厚が厚い。 In other words, in the present invention, each material of the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer is the same material in the anode side blue light emitting unit 5 and the cathode side red green light emitting unit 7. In the hole injection layer, the cathode-side red / green light-emitting unit 7 in contact with the connection layer 6 is thick, and in the electron injection layer, the anode-side blue light-emitting unit 5 in contact with the connection layer 6 is thick. The layer of the anode-side blue light-emitting unit 5 is thicker than the thickness of the cathode-side red-green light-emitting unit 7, and the electron transport layer is the film of the anode-side blue light-emitting unit 5 than the thickness of the cathode-side red-green light-emitting unit 7. Thick.
（白色発光有機ＥＬパネル）
本発明の白色発光有機ＥＬパネルは、本発明の白色発光有機ＥＬ素子１を含み、演色性のＲａ値、及びＲ９値が共に９０以上の白色光を発光する高演色性パネルとすることが好ましく、自然な色合いに観察者に観察せしめることができる照明を観察対象物に照射可能な照明光源とできる。
(White light emitting organic EL panel)
The white light-emitting organic EL panel of the present invention includes the white light-emitting organic EL element 1 of the present invention, and is a highly color-rendering panel that emits white light having a color rendering R a value and an R 9 value of 90 or more. It is preferable that the illumination light source capable of irradiating the observation object with illumination that allows the observer to observe natural colors.
また、本発明の白色発光有機ＥＬパネルは、色温度が３８００Ｋ以上の、より好ましくは、色温度が６０００Ｋ以下の白色光を発光する純白色性パネルとすることが好ましく、黄色や青色の色味を含まないより白色純度が高い発光となるので、前記観察対象物をより美しく照明可能である。 The white light-emitting organic EL panel of the present invention is preferably a pure white panel that emits white light having a color temperature of 3800K or more, more preferably 6000K or less, and has a yellow or blue color. Therefore, the observation object can be illuminated more beautifully.
さらに、本発明の白色発光有機ＥＬパネルは、前述の性質を兼ね備えた、高演色純白色性パネルとすることが好ましく、より高度な照明が可能となる。 Furthermore, the white light-emitting organic EL panel of the present invention is preferably a highly color-rendering pure white panel having the above-described properties, and more advanced illumination is possible.
（発光ユニット）
本発明に係るは、発光機能を有しており、有機化合物を主成分とし、かつ、実際にその層中で発光する発光層を含み、このような発光層が、その陽極層側の層から正孔を、その陰極層側の層から電子を、各々受け入れ可能な層をさらに含む、多層構造を有する。
(Light emitting unit)
According to the present invention, the light-emitting layer has a light-emitting function, includes an organic compound as a main component, and actually emits light in the layer. Such a light-emitting layer is formed from a layer on the anode layer side. It has a multilayer structure further including layers each accepting holes and electrons from the layer on the cathode layer side.
本発明の白色発光有機ＥＬ素子１は、このような発光ユニットとして、陽極側青発光ユニット５、及び陰極側赤緑発光ユニット７を含み、これら以外の発光ユニットを含むこともできる。 The white light-emitting organic EL element 1 of the present invention includes, as such a light-emitting unit, an anode-side blue light-emitting unit 5 and a cathode-side red-green light-emitting unit 7, and can also include other light-emitting units.
（正孔注入層）
本発明に係る正孔注入層は、例えば、本発明に係る陽極側青発光ユニット５の正孔注入層５１、本発明に係る陰極側赤緑発光ユニット７の正孔注入層７１であり、これを形成する材料としては、テトラシアノキノジメタン系化合物、酸化モリブデン（ＭｏＯ３）、酸化タングステン（ＷＯ３）、酸化バナジウム（Ｖ２Ｏ５）等が採用できる。また、正孔輸送性を有する化合物に上記材料を含有させたものも好ましく用いることができる。
(Hole injection layer)
The hole injection layer according to the present invention is, for example, the hole injection layer 51 of the anode-side blue light-emitting unit 5 according to the present invention and the hole injection layer 71 of the cathode-side red / green light-emitting unit 7 according to the present invention. As a material for forming, tetracyanoquinodimethane compounds, molybdenum oxide (MoO3), tungsten oxide (WO3), vanadium oxide (V2O5), and the like can be employed. Moreover, what mixed the said material in the compound which has hole transportability can also be used preferably.
（正孔輸送層）
本発明に係る正孔輸送層は、例えば、本発明に係る陽極側青発光ユニット５の正孔輸送層５２、本発明に係る陰極側赤緑発光ユニット７の正孔輸送層７２であり、これを形成する材料としては、正孔輸送性を有する化合物から適宜選択される。
(Hole transport layer)
The hole transport layer according to the present invention is, for example, the hole transport layer 52 of the anode-side blue light-emitting unit 5 according to the present invention and the hole transport layer 72 of the cathode-side red / green light-emitting unit 7 according to the present invention. As a material for forming, a compound having a hole transporting property is appropriately selected.
前記正孔輸送性材料としては、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（ＴＰＤ）、４，４’−ビス［Ｎ−（ナフチル）−Ｎ−フェニル−アミノ］ビフェニル（α−ＮＰＤ）、４，４’，４”−トリス（Ｎ−（３−メチルフェニル）Ｎ−フェニルアミノ）トリフェニルアミン（ＭＴＤＡＴＡ）、４，４’，４”−トリス〔Ｎ，Ｎ−（２−ナフチル）フェニルアミノ〕トリフェニルアミン（２−ＴＮＡＴＡ）、４，４’−Ｎ，Ｎ’−ジカルバゾールビフェニル（ＣＢＰ）、４，４′，４″−トリ（Ｎ−カルバゾリル）トリフェニルアミン（ＴＣＴＡ）、などのトリフェニルアミン系化合物、スターバースト型アミン系化合物、カルバゾール系化合物などが挙げられる。 Examples of the hole transporting material include N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD), 4,4′-bis [N— (Naphthyl) -N-phenyl-amino] biphenyl (α-NPD), 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (MTDATA), 4,4 ', 4 "-tris [N, N- (2-naphthyl) phenylamino] triphenylamine (2-TNATA), 4,4'-N, N'-dicarbazolebiphenyl (CBP), 4,4', Examples thereof include triphenylamine compounds such as 4 ″ -tri (N-carbazolyl) triphenylamine (TCTA), starburst amine compounds, and carbazole compounds.
（発光層）
本発明に係る発光層は、例えば、本発明に係る陽極側青発光ユニット５の青発光層５３、本発明に係る陰極側赤緑発光ユニット７の赤緑発光層７３である。
(Light emitting layer)
The light emitting layer according to the present invention is, for example, the blue light emitting layer 53 of the anode side blue light emitting unit 5 according to the present invention and the red green light emitting layer 73 of the cathode side red green light emitting unit 7 according to the present invention.
前記青発光層は、青色発光性材料がドープされたホスト材料として形成される。青発光層のホスト材料としては、ＴＢＡＤＮ（２−ｔ−ブチル−９，１０−ジ（２−ナフチル）アントラセン）、ＡＤＮ、ＢＤＡＦ、１，３−ビス（カルバゾール−９−イル）ベンゼン（ＭＣＰ）、４，４’−Ｎ，Ｎ’−ジカルバゾール−２，２’−ジメチルビフェニル（ＣＤＢＰ）、１，４−ビス（トリフェニルシリル）ベンゼン（ＵＧＨ２）、１，３−ビス（トリフェニルシリル）ベンゼン（ＵＧＨ３）などが挙げられる。 The blue light emitting layer is formed as a host material doped with a blue light emitting material. As a host material of the blue light emitting layer, TBADN (2-t-butyl-9,10-di (2-naphthyl) anthracene), ADN, BDAF, 1,3-bis (carbazol-9-yl) benzene (MCP) 4,4′-N, N′-dicarbazole-2,2′-dimethylbiphenyl (CDBP), 1,4-bis (triphenylsilyl) benzene (UGH2), 1,3-bis (triphenylsilyl) Examples include benzene (UGH3).
前記青色発光性材料としては、蛍光発光材料、燐光発光材料を用いることができる。蛍光発光材料としては、ペリレン、４，４′−ビス（９−エチル−３−カルバゾビニレン）−１，１−ビフェニル（ＢＣｚＶＢｉ）、４，４′−ビス［４−（ジ−ｐ−トリアミノ）スチリル］ビフェニル（ＤＰＡＶＢｉ）などが挙げられる。燐光発光材料としては、イリジウム錯体であるＦＩｒＰｉｃやＦＩｒ６などが挙げられる。 As the blue light emitting material, a fluorescent light emitting material or a phosphorescent light emitting material can be used. Fluorescent materials include perylene, 4,4'-bis (9-ethyl-3-carbazovinylene) -1,1-biphenyl (BCzVBi), 4,4'-bis [4- (di-p-triamino) styryl. ] Biphenyl (DPAVBi) and the like. Examples of the phosphorescent material include FIrPic and FIr6 which are iridium complexes.
前記赤緑発光層は、赤色発光材料及び緑色発光材料がドープされたホスト材料として形成される。赤緑発光層のホスト材料としては、Ａｌｑ３（トリス（８−オキソキノリン）アルミニウム（ＩＩＩ））、ＡＤＮ、ＢＤＡＦ、４，４’−Ｎ，Ｎ’−ジカルバゾールビフェニル（ＣＢＰ）、４，４′，４″−トリ（Ｎ−カルバゾリル）トリフェニルアミン（ＴＣＴＡ）、などが挙げられる。 The red / green light emitting layer is formed as a host material doped with a red light emitting material and a green light emitting material. As a host material of the red-green light emitting layer, Alq3 (tris (8-oxoquinoline) aluminum (III)), ADN, BDAF, 4,4′-N, N′-dicarbazole biphenyl (CBP), 4,4 ′ , 4 ″ -tri (N-carbazolyl) triphenylamine (TCTA), and the like.
前記緑色発光材料および赤色発光材料としては蛍光発光材料、燐光発光材料を用いることができる。蛍光発光材料としては、クマリン６、Ｃ５４５Ｔなどの緑色蛍光発光材料や、ルブレン、ＤＣＭ、ＤＣＭ２などの赤色蛍光発光材料が挙げられる。燐光発光材料としては、イリジウム錯体であるＩｒ（ｐｐｙ）３などの緑色燐光発光材料や、Ｂｔｐ２Ｉｒ（ａｃａｃ）、Ｉｒ（ｐｉｑ）３などの赤色燐光発光材料などが挙げられる。 As the green light emitting material and the red light emitting material, a fluorescent light emitting material or a phosphorescent light emitting material can be used. Examples of the fluorescent luminescent material include green fluorescent luminescent materials such as coumarin 6 and C545T, and red fluorescent luminescent materials such as rubrene, DCM, and DCM2. Examples of the phosphorescent material include green phosphorescent materials such as Ir (ppy) 3 which is an iridium complex, and red phosphorescent materials such as Btp2Ir (acac) and Ir (piq) 3 .
（電子輸送層）
本発明に係る電子輸送層は、例えば、本発明に係る陽極側青発光ユニット５の電子輸送層５４、本発明に係る陰極側赤緑発光ユニット７の電子輸送層７４であり、これを形成する材料としては、電子輸送性を有する化合物から適宜選択される。
(Electron transport layer)
The electron transport layer according to the present invention is, for example, the electron transport layer 54 of the anode-side blue light-emitting unit 5 according to the present invention and the electron transport layer 74 of the cathode-side red-green light-emitting unit 7 according to the present invention. The material is appropriately selected from compounds having electron transport properties.
前記電子輸送性材料としては、トリス（８−ヒドロキシキノリナート）アルミニウム（Ａｌｑ３）、ビス（２−メチル−８−キノリノラト）−４−フェニルフェノラト−アルミニウム（ＢＡｌｑ）、バソフェナントロリン（Ｂｐｈｅｎ）、バソクプロイン（ＢＣＰ）、トリアゾール誘導体、オキサジアゾール誘導体、シロール誘導体、フェニルキノキサリン誘導体などが挙げられる。 Examples of the electron transporting material include tris (8-hydroxyquinolinate) aluminum (Alq3), bis (2-methyl-8-quinolinolato) -4-phenylphenolato-aluminum (BAlq), bathophenanthroline (Bphen), Examples include bathocuproin (BCP), triazole derivatives, oxadiazole derivatives, silole derivatives, and phenylquinoxaline derivatives.
（電子注入層）
本発明に係る電子注入層は、例えば、本発明に係る陽極側青発光ユニット５の電子注入層５５、本発明に係る陰極側赤緑発光ユニット７の電子注入層７５であり、これを形成する材料としては、フッ化リチウム（ＬｉＦ）、フッ化セシウム（ＣｓＦ）、フッ化カルシウム（ＣａＦ２）等のようなアルカリ金属又はアルカリ土類金属の化合物等が採用できる。また、電子輸送性を有する物質からなる層中にアルカリ金属又はアルカリ土類金属を含有させたもの、例えばＡｌｑ３中にマグネシウム（Ｍｇ）を含有させたものなども好ましく用いることができる。
(Electron injection layer)
The electron injection layer according to the present invention is, for example, the electron injection layer 55 of the anode-side blue light-emitting unit 5 according to the present invention and the electron injection layer 75 of the cathode-side red / green light-emitting unit 7 according to the present invention. As the material, an alkali metal or alkaline earth metal compound such as lithium fluoride (LiF), cesium fluoride (CsF), or calcium fluoride (CaF 2 ) can be employed. A layer made of a substance having an electron transporting property containing an alkali metal or an alkaline earth metal, for example, a layer containing magnesium (Mg) in Alq3 can be preferably used.
（接続層６）
本発明に係る接続層は、例えば、本発明に係る接続層６であるが、本発明の白色発光有機ＥＬ素子１は、複数の接続層を含むことができ、また、前記接続層６も、本発明に係る陽極側青発光ユニット５と接する接続層６と、本発明に係る陰極側赤緑発光ユニット７と接する接続層６とが、同一の接続層である必要は必ずしも無く、別個の２つの接続層６であっても良いが、簡素な素子構造とする観点から、同一の接続層６であることが好ましく、接続層として接続層６を１個だけ含む白色発光有機ＥＬ素子１とすることがより好ましい。
(Connection layer 6)
The connection layer according to the present invention is, for example, the connection layer 6 according to the present invention, but the white light-emitting organic EL element 1 according to the present invention can include a plurality of connection layers, and the connection layer 6 also includes: The connection layer 6 in contact with the anode-side blue light-emitting unit 5 according to the present invention and the connection layer 6 in contact with the cathode-side red-green light-emitting unit 7 according to the present invention do not necessarily have to be the same connection layer. However, from the viewpoint of a simple device structure, the same connection layer 6 is preferable, and the white light-emitting organic EL device 1 including only one connection layer 6 is used as the connection layer. It is more preferable.
本発明に係る接続層は、本発明の白色発光有機ＥＬ素子１への通電時に、これに隣接する陽極側の発光ユニットに電子を注入し、かつ、これに隣接する陰極側発光ユニットに正孔を注入する機能を有する層であり、このような機能を有するのであれば、各種材料、例えば有機材料を用い、また、これらを組み合わせて用い、形成できる。 The connection layer according to the present invention injects electrons into the anode side light emitting unit adjacent to the white light emitting organic EL element 1 of the present invention, and holes to the cathode side light emitting unit adjacent thereto. As long as it has such a function, it can be formed using various materials such as organic materials, or a combination thereof.
本発明に係る接続層は、その透明性を向上させ輝度向上を図る観点、及び、その各電荷の注入性を向上させ電気特性向上を図る観点から、各々の電荷の注入層を組み合わせて用いることが好ましい。 In the connection layer according to the present invention, the charge injection layers are used in combination from the viewpoints of improving the transparency and improving the luminance, and improving the electric characteristics and improving the electric characteristics. Is preferred.
より好ましくは、各々の電荷の輸送性材料に、対応する電子受容性又は電子供与性ドーパントをドープした層とすることであり、例えば、正孔輸送性材料に電子受容性ドーパントをドープした正孔注入層と、電子輸送性材料に電子供与性ドーパントをドープした電子注入層を積層した構成とできる。接続層は、有機材料のみで構成することもできる。 More preferably, each charge transporting material is a layer doped with a corresponding electron accepting or electron donating dopant, for example, a hole transporting material doped with an electron accepting dopant. A structure in which an injection layer and an electron injection layer doped with an electron-donating dopant in an electron transporting material are stacked may be employed. The connection layer can also be composed of only an organic material.
このような接続層は、アルミニウムなどの金属材料や、透明導電性金属酸化物材料、適当な有機材料から適宜選択される。有機材料としては、電子輸送性の材料、ホール輸送性の材料、電子輸送性とホール輸送性とを併せ持つ材料の、いずれも使用することができる。 Such a connection layer is appropriately selected from metal materials such as aluminum, transparent conductive metal oxide materials, and appropriate organic materials. As the organic material, any of an electron transporting material, a hole transporting material, and a material having both electron transporting property and hole transporting property can be used.
（透光性絶縁基板２）
本発明に係る透光性絶縁基板２としては、透明であり、かつ、絶縁性を有しているものであれば、用いることができる。例えば、ガラス基板やフィルム基板などが好ましく、有機ＥＬ素子の使用用途に合わせて選択的に用いられる。
(Translucent insulating substrate 2)
As the translucent insulating substrate 2 according to the present invention, any substrate can be used as long as it is transparent and has insulating properties. For example, a glass substrate, a film substrate, etc. are preferable, and it is selectively used according to the use application of an organic EL element.
（透光性陽極層３）
本発明に係る透光性陽極層３の材料は、透明であり、かつ、導電性を有しているものであれば、用いることができる。例えば、インジウム錫酸化物（ＩＴＯ）、インジウム亜鉛酸化物（ＩＺＯ）、酸化錫（ＳｎＯ２）、酸化亜鉛（ＺｎＯ）などの透明導電性酸化物が主に用いられる。本明細書の実施例では、ＩＴＯを用いている。ＩＴＯは透過性が高く、有機ＥＬ発光層からの光を外部へと取り出すことに優れているため、一般的に有機ＥＬ素子に広く用いられている。
(Translucent anode layer 3)
The material of the translucent anode layer 3 according to the present invention can be used as long as it is transparent and has conductivity. For example, transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), and zinc oxide (ZnO) are mainly used. In the examples of this specification, ITO is used. ITO is widely used in organic EL elements because it has high transparency and is excellent in extracting light from the organic EL light emitting layer to the outside.
（陽極側青発光ユニット５）
本発明に係る陽極側青発光ユニット５は、順に、正孔注入層５１、正孔輸送層５２、青発光層５３、電子輸送層５４、及び電子注入層５５を含み、前記青発光層５３として、寿命が長い素子とする観点から、青蛍光発光層５３を含むことが好ましい。青蛍光発光層は、青色蛍光材料、及びホスト材料を含む。
(Anode-side blue light-emitting unit 5)
The anode-side blue light-emitting unit 5 according to the present invention includes a hole injection layer 51, a hole transport layer 52, a blue light-emitting layer 53, an electron transport layer 54, and an electron injection layer 55 in this order. From the viewpoint of obtaining a device having a long lifetime, it is preferable to include the blue fluorescent light-emitting layer 53. The blue fluorescent light emitting layer includes a blue fluorescent material and a host material.
前記青発光層５３に含有される青色発光材料の発光極大波長は、４５０〜４９０ｎｍであることが好ましい。 The emission maximum wavelength of the blue light emitting material contained in the blue light emitting layer 53 is preferably 450 to 490 nm.
本明細書の実施例では、陽極側青発光ユニット５は、その発光層として、青発光層５３のみを含むが、その他の色の発光層が含まれていてもよく、好ましくは青色に近い波長を持つ色、即ち、青緑色や緑色の発光色を持つ発光層が、前記青発光層５３と共に、発光層として含めることで、青色を補助する発光色としてもよい。発光色が多数になるほどより色鮮やかに発光する素子を得ることができる。 In the examples of the present specification, the anode-side blue light-emitting unit 5 includes only the blue light-emitting layer 53 as the light-emitting layer, but may include other light-emitting layers, and preferably has a wavelength close to blue. A light emitting layer having a blue color, that is, a light emitting color having a blue-green color or a green light emitting color, may be included as a light emitting layer together with the blue light emitting layer 53 to thereby provide a light emitting color that assists blue. As the number of emission colors increases, an element that emits light more vividly can be obtained.
（陰極側赤緑発光ユニット７）
本発明に係る陰極側赤緑発光ユニット７は、順に、正孔注入層７１、正孔輸送層７２、赤緑発光層７３、電子輸送層７４、及び電子注入層７５を含み、輝度が大きい素子とする観点から、赤緑燐光発光層７３を含むことが好ましい。赤緑燐光発光層は、赤色燐光材料、緑色燐光材料、及びホスト材料を含み、高演色性の素子とする観点から、赤色燐光材料と、緑色燐光材料との最大発光ピーク波長が、６０ｎｍ以上離れていることがより好ましい。
(Cathode side red / green light emitting unit 7)
The cathode-side red / green light emitting unit 7 according to the present invention includes a hole injection layer 71, a hole transport layer 72, a red / green light emission layer 73, an electron transport layer 74, and an electron injection layer 75 in this order, and has a high luminance. From the viewpoint of, it is preferable to include the red-green phosphorescent light-emitting layer 73. The red-green phosphorescent light-emitting layer includes a red phosphorescent material, a green phosphorescent material, and a host material, and from the viewpoint of obtaining a high color rendering element, the maximum emission peak wavelength between the red phosphorescent material and the green phosphorescent material is 60 nm or more apart. More preferably.
例えば、前記赤緑発光層７３に含有される緑色発光材料と赤色発光材料の発光極大波長は、それぞれ５００〜５８０ｎｍ、５９０〜６３０ｎｍであることが好ましく、緑色発光材料と赤色発光材料とは、単一の発光層内に混合して含有されていることが好ましい。発光層が単一であることにより、複数層である場合と比較して経時変化による色変化が起こりづらい。これは、正孔と電子の再結合領域がシフトした場合に、複数の発光層では、シフトした側の発光層からの発光が強まり、逆側の発光層からの発光が弱まることにより色変化が起こることに対して、単一の発光層である場合、再結合領域がシフトすることによる色変化は起こらないからである。 For example, the light emission maximum wavelengths of the green light emitting material and the red light emitting material contained in the red / green light emitting layer 73 are preferably 500 to 580 nm and 590 to 630 nm, respectively. It is preferable that they are mixed and contained in one light emitting layer. Due to the single light emitting layer, color change due to changes with time is less likely to occur than in the case of multiple layers. This is because, when the recombination region of holes and electrons is shifted, in a plurality of light emitting layers, light emission from the light emitting layer on the shifted side becomes stronger, and light emission from the light emitting layer on the opposite side becomes weaker. This is because, in the case of a single light emitting layer, color change due to the shift of the recombination region does not occur.
（反射性陰極層４）
本発明に係る反射性陰極層４としては、光反射性、及び導電性を有しているものであれば用いることができ、反射率の高い金属材料が好ましく用いられ、より好ましくは、銀、又は、アルミニウムである。
(Reflective cathode layer 4)
As the reflective cathode layer 4 according to the present invention, any material having light reflectivity and conductivity can be used, and a metal material having high reflectance is preferably used, and more preferably silver, Or it is aluminum.
以下、実施例により本発明を具体的に説明する。なお本発明は、以下の実施例に限定されるものではなく、その要旨を変更しない範囲で適宜変更して実施することができる。 Hereinafter, the present invention will be described specifically by way of examples. In addition, this invention is not limited to a following example, In the range which does not change the summary, it can change suitably and can implement.
（実施例１）
まず、ガラス基板上にインジウム錫酸化物（以下、ＩＴＯと略す）膜が１２０ｎｍ形成された透明電極付き基板の当該ＩＴＯ膜をパターニングすることで、素子形成用基板を作製した。
Example 1
First, an element forming substrate was fabricated by patterning the ITO film of a substrate with a transparent electrode in which an indium tin oxide (hereinafter abbreviated as ITO) film of 120 nm was formed on a glass substrate.
次に、前記素子形成用基板のパターニングしたＩＴＯ膜３上に、真空蒸着法を用いて、陽極側青発光ユニット５、接続層６、陰極側赤緑発光ユニット７、反射性陰極層４を順に成膜することで、実施例１の白色発光有機ＥＬ素子１を作製した。 Next, the anode side blue light emitting unit 5, the connection layer 6, the cathode side red green light emitting unit 7, and the reflective cathode layer 4 are sequentially formed on the patterned ITO film 3 of the element forming substrate by using a vacuum deposition method. By forming the film, the white light-emitting organic EL element 1 of Example 1 was produced.
実施例１の陽極側青発光ユニット５と陰極側赤緑発光ユニット７は、両ユニット共に正孔注入層、正孔輸送層、発光層、電子輸送層、電子注入層を含み、陽極側青発光ユニット５の発光層５３は、青色蛍光材料を、その青発光スペクトルが４６５ｎｍに最大発光ピーク波長を有する材料とし、ホスト材料と共蒸着することにより平均厚み２２ｎｍで形成した。陰極側赤緑発光ユニット７の発光層７３は、緑色燐光材料を、その緑発光スペクトルが５６０ｎｍに最大発光ピークを有する材料とし、赤色燐光材料を、その赤発光スペクトルが６２５ｎｍに最大発光ピークを有する材料とし、緑色燐光材料と赤色燐光材料とホスト材料の３源共蒸着により、平均厚み４０ｎｍで形成した。 The anode side blue light emitting unit 5 and the cathode side red green light emitting unit 7 of Example 1 both include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. The light-emitting layer 53 of the unit 5 was formed with a blue fluorescent material having a maximum emission peak wavelength at 465 nm as a blue emission spectrum and co-evaporated with a host material to an average thickness of 22 nm. The light emitting layer 73 of the cathode-side red / green light emitting unit 7 uses a green phosphorescent material whose green emission spectrum has a maximum emission peak at 560 nm, and a red phosphorescent material whose red emission spectrum has a maximum emission peak at 625 nm. As a material, a three-source co-evaporation of a green phosphorescent material, a red phosphorescent material, and a host material was formed with an average thickness of 40 nm.
さらに、同一の正孔輸送材料、及び電子受容性材料からなる正孔注入層を陽極側青発光ユニット５では平均厚み１４ｎｍ、陰極側赤緑発光ユニット７では平均厚み２０ｎｍで形成し、同一の電子輸送材料、及び電子供与性材料からなる電子注入層を陽極側青発光ユニット５では平均厚み２０ｎｍ、陰極側赤緑発光ユニット７では平均厚み１５ｎｍで形成し、同一の正孔輸送材料からなる正孔輸送層を陽極側青発光ユニット５では平均厚み６０ｎｍ、陰極側赤緑発光ユニット７では平均厚み２０ｎｍで形成し、同一の電子輸送材料からなる電子輸送層を陽極側青発光ユニット５では平均厚み２０ｎｍ、陰極側赤緑発光ユニット７では平均厚み１０ｎｍで形成した。 Further, a hole injection layer made of the same hole transport material and electron accepting material is formed with an average thickness of 14 nm in the anode side blue light emitting unit 5 and an average thickness of 20 nm in the cathode side red light emitting unit 7, and the same electron. An electron injection layer made of a transport material and an electron-donating material is formed with an average thickness of 20 nm in the anode-side blue light-emitting unit 5 and an average thickness of 15 nm in the cathode-side red-green light-emitting unit 7, and is made of the same hole-transport material. The transport layer is formed with an average thickness of 60 nm in the anode-side blue light-emitting unit 5, and the cathode-side red-green light-emitting unit 7 with an average thickness of 20 nm. The electron-transport layer made of the same electron transport material is formed with the average thickness of 20 nm in the anode-side blue light-emitting unit 5. The cathode-side red / green light emitting unit 7 was formed with an average thickness of 10 nm.
反射性陰極層４は、Ａｇを蒸着層として平均厚み１００ｎｍの膜厚で形成した。 The reflective cathode layer 4 was formed with an average thickness of 100 nm using Ag as a vapor deposition layer.
（実施例２）
実施例１の作製手順において、同一の電子輸送材料からなる電子輸送層を陽極側青発光ユニット５では平均厚み３０ｎｍ、陰極側赤緑発光ユニット７では平均厚み１０ｎｍで形成した。他の作製手順は、実施例１と同様である。
(Example 2)
In the production procedure of Example 1, an electron transport layer made of the same electron transport material was formed with an average thickness of 30 nm in the anode-side blue light-emitting unit 5 and an average thickness of 10 nm in the cathode-side red-green light-emitting unit 7. Other manufacturing procedures are the same as those in the first embodiment.
（比較例１）
実施例１の作製手順において、同一の電子輸送材料からなる電子輸送層を陽極側青発光ユニット５では平均厚み１０ｎｍ、陰極側赤緑発光ユニット７では平均厚み１０ｎｍで形成した。他の作製手順は、実施例１と同様である。
(Comparative Example 1)
In the production procedure of Example 1, an electron transport layer made of the same electron transport material was formed with an average thickness of 10 nm in the anode-side blue light-emitting unit 5 and an average thickness of 10 nm in the cathode-side red-green light-emitting unit 7. Other manufacturing procedures are the same as those in the first embodiment.
（比較例２）
実施例１の作製手順において、同一の電子輸送材料からなる電子輸送層を陽極側青発光ユニット５では平均厚み４０ｎｍ、陰極側赤緑発光ユニット７では平均厚み１０ｎｍで形成した。他の作製手順は、実施例１と同様である。
(Comparative Example 2)
In the production procedure of Example 1, an electron transport layer made of the same electron transport material was formed with an average thickness of 40 nm in the anode-side blue light-emitting unit 5 and an average thickness of 10 nm in the cathode-side red-green light-emitting unit 7. Other manufacturing procedures are the same as those in the first embodiment.
（実験結果）
各実施例および比較例の有機ＥＬ素子を３ｍＡ／ｃｍ２の定電流を通電し、分光放射系輝度計ＣＳ−１０００（コニカミノルタセンシング社製）を用いて測定することで、色温度、演色評価数を評価した。結果として得られた色温度、演色評価数Ｒａ、特殊演色評価数Ｒ９を表１に示す。
(Experimental result)
By applying a constant current of 3 mA / cm 2 to the organic EL elements of the examples and comparative examples and measuring using a spectral radiation system luminance meter CS-1000 (manufactured by Konica Minolta Sensing), color temperature and color rendering evaluation Number was evaluated. The resulting color temperature, the color rendering index R a , and the special color rendering index R 9 are shown in Table 1.
表１から判るように、実施例１および実施例２によると、３８００Ｋ以上の高色温度の白色発光をし、かつ、ＲａおよびＲ９がともに９０以上の高い値である有機ＥＬ素子を得ることができた。 As can be seen from Table 1, according to Example 1 and Example 2, an organic EL device that emits white light at a high color temperature of 3800 K or higher and has Ra and R 9 both as high as 90 or higher is obtained. I was able to.
１．白色発光有機ＥＬ素子
２．透光性絶縁基板
３．透光性陽極層
４．反射性陰極層
５．陽極側青発光ユニット
６．接続層
７．陰極側赤緑発光ユニット
５１．陽極側青発光ユニット正孔注入層
５２．陽極側青発光ユニット正孔輸送層
５３．陽極側青発光ユニット青発光層
５４．陽極側青発光ユニット電子輸送層
５５．陽極側青発光ユニット電子注入層
７１．陰極側赤緑発光ユニット正孔注入層
７２．陰極側赤緑発光ユニット正孔輸送層
７３．陰極側赤緑発光ユニット赤緑発光層
７４．陰極側赤緑発光ユニット電子輸送層
７５．陰極側赤緑発光ユニット電子注入層
1. White light-emitting organic EL device 2. Translucent insulating substrate 3. Translucent anode layer 4. Reflective cathode layer 5. Anode-side blue light emitting unit Connection layer 7. Cathode side red / green light emitting unit 51. 52. Anode-side blue light emitting unit hole injection layer Anode-side blue light emitting unit hole transport layer 53. Anode side blue light emitting unit blue light emitting layer 54. Anode side blue light emitting unit electron transport layer 55. 71. Anode-side blue light emitting unit electron injection layer Cathode side red / green light emitting unit hole injection layer 72. Cathode-side red / green light emitting unit hole transport layer 73. Cathode side red / green light emitting unit red / green light emitting layer 74. Cathode-side red-green light emitting unit electron transport layer 75. Cathode side red / green light emitting unit electron injection layer
Claims (4)
該陽極側青発光ユニット、及び該陰極側赤緑発光ユニットの各々が、該透光性陽極層側から正孔注入層、正孔輸送層、発光層、電子輸送層、及び電子注入層を含み、
両ユニットの、
正孔注入層が、同一の、正孔輸送材料、及び電子受容性材料からなり、かつ、陰極側赤緑発光ユニット正孔注入層厚みが、陽極側青発光ユニット正孔注入層厚みの１．２倍以上、２倍以下であり、
正孔輸送層が、同一の正孔輸送材料からなり、かつ、陽極側青発光ユニット正孔輸送層厚みが、陰極側赤緑発光ユニット正孔輸送層厚みの２倍以上、４倍以下であり、
電子輸送層が、同一の電子輸送材料からなり、かつ、陽極側青発光ユニット電子輸送層厚みが、陰極側赤緑発光ユニット電子輸送層厚みの２倍以上、４倍以下であり、さらに、
電子注入層が、同一の、電子輸送材料、及び電子供与性材料からなり、かつ、陽極側青発光ユニット電子注入層厚みが、陰極側赤緑発光ユニット電子注入層厚みの１．２倍以上、２倍以下である、白色発光有機ＥＬ素子。 A white light-emitting organic EL element formed of a light-transmitting anode layer, an anode-side blue light-emitting unit, a connection layer, a cathode-side red-green light-emitting unit, and a reflective cathode layer, which are sequentially formed on a light-transmitting insulating substrate,
Each of the anode-side blue light-emitting unit and the cathode-side red-green light-emitting unit includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer from the translucent anode layer side. ,
Of both units,
1. The hole injection layer is made of the same hole transport material and electron accepting material, and the cathode side red / green light emitting unit hole injection layer thickness is 1. 2 times or more, 2 times or less,
The hole transport layer is made of the same hole transport material, and the anode side blue light emitting unit hole transport layer thickness is 2 to 4 times the cathode side red green light emitting unit hole transport layer thickness. ,
The electron transport layer is made of the same electron transport material, and the anode-side blue light-emitting unit electron transport layer thickness is 2 to 4 times the cathode-side red / green light-emitting unit electron transport layer thickness;
The electron injection layer is made of the same electron transport material and electron donating material, and the anode side blue light emitting unit electron injection layer thickness is 1.2 times or more of the cathode side red green light emitting unit electron injection layer thickness, A white light-emitting organic EL device that is twice or less.
演色性のＲａ値、及びＲ９値が共に９０以上の白色光を発光し、かつ、
前記赤色燐光材料と、前記緑色燐光材料との最大発光ピーク波長が、６０ｎｍ以上離れている、白色発光有機ＥＬパネル。 A white light-emitting organic EL panel comprising the white light-emitting organic EL element according to claim 2,
Emits white light with a Ra value of color rendering properties and an R 9 value of 90 or more, and
A white light emitting organic EL panel in which a maximum emission peak wavelength between the red phosphorescent material and the green phosphorescent material is 60 nm or more apart.
色温度が３８００Ｋ以上の白色光を発光する、白色発光有機ＥＬパネル。 A white light-emitting organic EL panel comprising the white light-emitting organic EL element according to claim 2,
A white light-emitting organic EL panel that emits white light having a color temperature of 3800K or higher.
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