KR102081011B1 - Organic electroluminescent device, manufacturing method of organic electroluminescent device, display device, lighting device and organic electroluminescent device material - Google Patents

Abstract

(R은 알킬기, 할로겐 원자, 알콕시기, 아릴옥시기, 알킬티오기, 아릴티오기, 아실기, 술피닐기, 술포닐기, 니트로기, 시아노기, 히드록시기 또는 머캅토기, Ar은 방향족 탄화수소기 또는 방향족 복소환기, X₁-L₁-X₂는 2좌의 배위자, 인접하는 R₁ 내지 R₄ 중 2개는 일반식 (2) 내지 (4) 중 어느 것을 나타낸다.)

(Y₁ 내지 Y₄는 O, S 또는 N-R', Y₅ 또는 Y₆은 CR" 또는 N, Z₁ 내지 Z₈은 C-Rx 또는 N을 나타낸다.)Provided is an organic EL device having a light emission ratio of a component having a longer wavelength than the maximum light emission wavelength, high light emission efficiency, low driving voltage and long light emission lifetime, small voltage rise during driving, and excellent stability over time. The organic EL device includes an organic layer sandwiched between an anode and a cathode, and contains a compound having a structure in which at least one of the organic layers is represented by the general formula (1).

(R is an alkyl group, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfinyl group, sulfonyl group, nitro group, cyano group, hydroxy group or mercapto group, Ar is aromatic hydrocarbon group or aromatic A heterocyclic group, X ₁ -L ₁ -X ₂ represents a bidentate ligand, two of adjacent R ₁ to R ₄ represent any of General Formulas (2) to (4).)

(Y ₁ to Y ₄ represents O, S or N-R ', Y ₅ or Y ₆ represents CR "or N, Z ₁ to Z ₈ represents C-Rx or N.)

Description

Organic electroluminescent device, manufacturing method of organic electroluminescent device, display device, lighting device and organic electroluminescent device material

The present invention relates to an organic electroluminescent device, a method for producing an organic electroluminescent device, a display device, a lighting device, and an organic electroluminescent device material. In particular, the present invention is an organic electroluminescent device having a light emission ratio of a component having a longer wavelength than the maximum light emission wavelength, high light emission efficiency, low driving voltage and long light emission lifetime, small voltage rise during driving, and excellent stability over time. The present invention relates to a method for producing the device, a display device and a lighting device provided with the device, and an organic electroluminescent device material used for the device.

An organic electroluminescent element (hereinafter referred to as an "organic EL element") is a thin film type all-solid element composed of an organic thin film layer (single layer or multilayer) containing an organic light emitting material between an anode and a cathode. to be.

When a voltage is applied to the organic EL element, electrons are injected from the cathode to the organic thin film layer, holes are injected from the anode, and these are recombined in the light emitting layer (organic light emitting material-containing layer) to generate excitons. An organic EL element is a light emitting element utilizing the emission (fluorescence and phosphorescence) of light from these excitons, and is a technology expected as a next-generation flat panel display and lighting.

In addition, since the organic EL device using phosphorescence emission from the excitation triplet, which can achieve a light emission efficiency of about four times as compared with the organic EL device using fluorescent light emission, has been reported from Princeton University, a material exhibiting phosphorescence at room temperature In addition to the development of the present invention, the layer structure of the light emitting device and the research and development of the electrode have been conducted all over the world.

As described above, although the phosphorescent light emitting method is a very high potential method, in organic EL devices using phosphorescent light emission, a method of controlling the position of the emission center is largely different from that using fluorescent light emission, particularly in the inside of the light emitting layer. In order to improve light emission efficiency and lifespan of the organic EL device, it is important to know how light emission can be performed stably.

Therefore, a multilayer stacked element comprising a hole transporting layer located on the anode side of the light emitting layer, an electron transporting layer located on the cathode side of the light emitting layer, and the like, and a mixed layer containing a phosphorescent dopant and a host compound in the light emitting layer. The device which uses is developed.

From a material viewpoint, heavy metal complexes, such as an iridium complex system, are examined as a material which shows phosphorescence at room temperature. For example, although tris (2-phenylpyridine) iridium complex is widely known, sufficient device performance including a light emission lifetime has not been obtained. As the tris (2-phenylpyridine) iridium complex, an iridium complex having a phenylimidazole ligand or a carbene ligand is known. In these ligands, the light emission wavelength of the light emitting material is shortened to achieve blue color, and the light emission efficiency and the light emission lifetime have been greatly improved.

However, in recent years, an illumination light source having a high color temperature and a display having a wide color gamut are required, and a smaller y value measured using CIE coordinates is required. In order to achieve these, it is conceivable to make the maximum wavelength of light emission shorter and to reduce the long-wave component of light emission. Although shortening of the maximum wavelength of light emission has been examined variously, such as a change of a substituent, the shortening of the wavelength can be achieved to some extent, and the luminous efficiency and light emission lifetime of an element deteriorate drastically, and therefore the trade-off is improved. Was being asked.

Phenyltriazole is known as a ligand which shows blue light emission (for example, refer patent document 1). By these compounds, shortening of the maximum wavelength of light emission can be achieved, but the light emission lifetime and the light emission efficiency were not sufficient values.

On the other hand, the metal complex which the triazole ligand which the ring couple | bonded with the metal atom by the carbon atom has a condensed ring structure is known (for example, refer patent document 2, 3). Moreover, the metal complex which has the triazole ligand which the ring coordinated to the metal atom has the alkyl group in the adjacent position of the coordinating atom is known (for example, refer patent document 4). Although these compounds can achieve some improvement in the emission lifetime, there is room for further improvement.

International Publication No. 2004/101707 Japanese Patent No. 5644050 Japanese Patent No. 5090413 Japanese Patent Publication No. 2013-040159

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and situations, and a problem to be solved is that the emission ratio of components having a longer wavelength than the maximum emission wavelength is small, high light emission efficiency, low drive voltage, and long light emission lifetime, and the increase in voltage during driving is achieved. The present invention provides a small organic electroluminescent device excellent in stability over time, a method of manufacturing the device, a display device and a lighting device provided with the device, and an organic electroluminescent device material used for the device.

In order to solve the above problems according to the present invention, the causes of the problems and the like have been studied. As a result, a ring in which a metal complex having a 1H-1,2,4-triazole derivative as a ligand is bonded to a metal atom at a carbon atom is a hetero atom. The ring having a condensed structure and having a ring coordinating to a metal atom has a specific substituent at a position adjacent to the coordinating atom, so that light emission longer than the maximum emission wavelength can be suppressed, while maintaining a short emission maximum wavelength to some extent. It has been found that the luminous efficiency and luminous lifetime can be improved. That is, according to the present invention, by suppressing the emission of long waves and reducing the y value measured using the CIE coordinates, the organic EL device does not cause shortening of the maximum wavelength of light emission and a tradeoff of the luminous efficiency and emission life of the device. Can be provided.

That is, the present inventors found that the organic layer contains a compound having a structure represented by the following general formula (1), whereby the emission ratio of the component having a longer wavelength than the maximum emission wavelength is smaller, the emission efficiency is high, the driving voltage is low, and the long lifespan. It has been found that an organic electroluminescent device having a small voltage rise during driving and excellent stability over time can be provided.

The problem which concerns on this invention is solved by the following means.

1. An organic electroluminescent device comprising an organic layer sandwiched by at least one pair of anodes and cathodes,

An organic electroluminescent device, wherein said organic layer comprises at least one layer comprising a light emitting layer, and at least one of said organic layers contains a compound having a structure represented by the following general formula (1).

(In General Formula (1), R represents an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxyl group, and a mercapto group. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group R ₁ to R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, a heterocyclic group, or an aromatic heterocyclic group Ventilation, halogen atom, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, ureide group, acyl group, acyloxy group , Amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, nitro group, cyano group, hydroxy group, mercapto group, alkylsilyl group, arylsilyl group, alkyl phosphino group, ar Phosphino group, a phosphonic group, an aryl phosphonate group, alkylthio phosphorylation represents one selected from an aryl group and a phosphonium group-thio group.

X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ . m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n is 3.

However, at least 2 of adjacent R <_1> -R <_4> condenses and represents any structure of following General formula (2)-(4).)

(In General Formulas (2) to (4), Y ₁ to Y ₄ each independently represent O, S, or N—R ′, and Y ₅ or Y ₆ represents CR ″ or N. R ′ represents an alkyl group, Any group selected from a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group and an aromatic heterocyclic group, R "represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, a cyano group, Represents any group selected from an arylsilyl group and an arylphosphoryl group Z ₁ to Z ₈ each independently represent C-Rx or N, and a plurality of Rx's may be the same as or different from each other. The group equivalent to R <_1> -R < ₄ > in the said General formula (1) is represented. * Represents a coupling | bonding position with the structure represented by the said General formula (1).)

2. The structure represented by the said General formula (1) is a structure represented by either of following General formula (5)-(10), The organic electroluminescent element of 1st term | claim characterized by the above-mentioned.

(In Formulas (5) to (10), R, Ar, R ₁ to R ₄ , Y ₁ , Z ₁ to Z ₄ , X ₁ , X ₂ , L ₁ , m, and n are the general formulas (1) And (2) the same meaning as R, Ar, R ₁ to R ₄ , Y ₁ , Z ₁ to Z ₄ , X ₁ , X ₂ , L ₁ , m and n.)

3. In said general formula (1), at least 2 of adjacent R <_1> -R <_4> condenses and represents the structure of said General formula (3) or (4), The organic electroluminescent of Claim 1 characterized by the above-mentioned. Nessence element.

4. The organic electroluminescent device according to any one of items 1 to 3, wherein R represents an alkyl group or a cyano group.

5. In said general formula (1), Ar represents the aromatic-hydrocarbon group or aromatic heterocyclic group which has a substituent in 2-position, The organic electroluminescence in any one of Claims 1-4 characterized by the above-mentioned. device.

6. In said general formula (1), n represents 0, The organic electroluminescent element as described in any 1 item | term from 1st term | claim characterized by the above-mentioned to 5th term | claim.

7. The organic electroluminescent device according to any one of items 1 to 6, wherein the light emitting layer contains a compound having a structure represented by the general formula (1).

8. The organic electroluminescent device according to item 7, wherein the light emitting layer contains at least two kinds of the compound of the general formula (1) and a compound having a HOMO level of -5.4 eV or less.

9. It is a manufacturing method of the organic electroluminescent element which manufactures the organic electroluminescent element of any one of Claims 1-8.

The manufacturing method of the organic electroluminescent element characterized by forming the layer containing the compound which has a structure represented by the said General formula (1) among the said organic layers by a wet process.

10. A display device comprising the organic electroluminescent element according to any one of items 1 to 8.

11. An illumination device comprising the organic electroluminescent element according to any one of items 1 to 8.

12. An organic electroluminescent device material characterized by containing a compound having a structure represented by the following general formula (1).

(In General Formula (1), R represents an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxyl group, and a mercapto group. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group R ₁ to R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, a heterocyclic group, or an aromatic heterocyclic group Ventilation, halogen atom, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, ureide group, acyl group, acyloxy group , Amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, nitro group, cyano group, hydroxy group, mercapto group, alkylsilyl group, arylsilyl group, alkyl phosphino group, ar Phosphino group, a phosphonic group, an aryl phosphonate group, alkylthio phosphorylation represents one selected from an aryl group and a phosphonium group-thio group.

X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ . m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n is 3.

However, at least 2 of adjacent R <_1> -R <_4> condenses and represents any structure of following General formula (2)-(4).)

(In General Formulas (2) to (4), Y ₁ to Y ₄ each independently represent O, S, or N—R ′, and Y ₅ or Y ₆ represents CR ″ or N. R ′ represents an alkyl group, Any group selected from a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group and an aromatic heterocyclic group, R "represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, a cyano group, Represents any group selected from an arylsilyl group and an arylphosphoryl group Z ₁ to Z ₈ each independently represent C-Rx or N, and a plurality of Rx's may be the same as or different from each other. The group equivalent to R <_1> -R < ₄ > in the said General formula (1) is represented. * Represents a coupling | bonding position with the structure represented by the said General formula (1).)

According to the present invention, an organic electroluminescent device having a light emission ratio of a component having a longer wavelength than a maximum light emission wavelength, high light emission efficiency, low driving voltage, and long light emission lifetime, small voltage rise during driving, and excellent stability over time and The organic electroluminescent element material used for the said element can be provided. In addition, the production aptitude by the wet process of the device can be improved. Moreover, the lighting device and display device provided with the said element can be provided.

Although it is not clear about the expression mechanism of the effect of this invention, or a mechanism of action, it estimates as follows.

The compound having the structure represented by the general formula (1) has 1H-1,2,4 in which a ring bonded to a metal atom at a carbon atom has a condensed ring structure, and a ring coordinating at a metal atom has a substituent specific to an adjacent position of the coordinating atom. It is a metal complex which has a triazole derivative as a ligand. MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, it turned out that the ring couple | bonded with the carbon atom to the metal atom has a condensed structure containing a hetero atom, and the effect which suppresses light emission of the component which is longer than the maximum light emission wavelength is shown.

This is because the ring bonded to the metal atom at the carbon atom is condensed, so that the deformation of the ring structure in the excited state is suppressed, and since the hetero atom is included in the condensed ring structure, the structure is more rigid. I guess. However, having a condensed structure widens the? Plane and tends to aggregate, so that the light emission is broadened and the effect cannot be sufficiently exhibited. Here, the present inventors further show that the ring coordinated to a metal atom has a substituent (R in the general formula (1) of the present invention) specified in the adjacent position of the coordinating atom, whereby aggregation is suppressed and the vibration of the ligand is also increased. By suppressing, it was found that the effect of suppressing the light emission of a component having a longer wave than the maximum wavelength of light emission appeared more remarkably.

In addition, the compound having the structure represented by the general formula (1) not only exhibits the effect of suppressing light emission of components having a longer wavelength than the maximum light emission wavelength, but also has high luminous efficiency, low driving voltage and long life, and It is possible to provide an organic EL device having a small voltage rise and excellent stability over time. This is because a compound having a structure represented by the general formula (1) has a rigid structure in which a ring bonded at a carbon atom to a metal atom has a heterocyclic structure containing a hetero atom, so that deformation occurs even when it is excited. It is thought to be because the crystallinity is also suppressed by having a substituent at a specific position, thereby increasing the stability of the compound itself and hardly causing crystallization or decomposition over time. Thereby, it became possible to provide the organic electroluminescent element which is long life and is small in the voltage rise at the time of drive, and is excellent with time stability. Moreover, since the compound which has a structure represented by General formula (1) improves charge transport property unlike an aromatic condensed ring, fluorene, etc., since the ring couple | bonded at the carbon atom to the metal atom contains a hetero atom, light emission efficiency is improved. This high and low drive voltage can be achieved.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which showed an example of the display apparatus comprised from organic electroluminescent element.
2 is a schematic view of the display portion A in FIG. 1.
3 is a schematic diagram showing a circuit of a pixel;
FIG. 4 is a schematic diagram of a passive matrix system full color display device according to the display portion A of FIG. 2.
5 is a schematic view of a lighting device.
6 is a sectional view of the lighting apparatus.
7A is a schematic configuration diagram of an organic EL full color display device.
7B is a schematic configuration diagram of an organic EL full color display device.
7C is a schematic configuration diagram of an organic EL full color display device.
7D is a schematic configuration diagram of an organic EL full color display device.
Fig. 7E is a schematic configuration diagram of an organic EL full color display device.

The organic electroluminescent device of the present invention is an organic electroluminescent device having an organic layer sandwiched by at least one pair of anodes and cathodes, the organic layer including at least one layer including a light emitting layer, and among the organic layers At least one layer contains the compound which has a structure represented by the said General formula (1), It is characterized by the above-mentioned. This feature is a common or corresponding technical feature in each claim.

In this invention, it is preferable that the structure represented by the said General formula (1) is a structure represented by any of the said General formulas (5)-(10).

Moreover, in this invention, it is preferable in the said General formula (1) that at least 2 of adjacent R <_1> -R <_4> condenses and represents the structure of said General formula (3) or (4).

In addition, in this invention, it is preferable that R represents an alkyl group or a cyano group in the said General formula (1). As a result, since R has an appropriate size, the effect of suppressing vibration of the ligand is improved, and light emission of a component having a longer wave than the maximum wavelength of light emission can be suppressed more effectively.

In the present invention, in General Formula (1), Ar preferably represents an aromatic hydrocarbon group or an aromatic heterocyclic group having a substituent at the 2-position. Thereby, expansion of the conjugated system with the ring coordinated to the metal atom can be cut off, and long wavelength of the light emission wavelength can be suppressed.

In addition, in this invention, it is preferable that n represents 0 in the said General formula (1). As a result, since light emission from the same ligand is obtained, the waveform of light emission is sharp, and light emission of components having a longer wavelength than the light emission maximum wavelength can be suppressed more effectively.

Moreover, in this invention, it is preferable that the said light emitting layer contains the compound which has a structure represented by the said General formula (1).

Moreover, in this invention, it is preferable that the said light emitting layer contains the compound of the said General formula (1), and at least 2 type of a compound whose HOMO level is -5.4 eV or less. The compound having the structure represented by the general formula (1) according to the present invention has a deep HOMO level compared with a metal complex having a 4H-1,2,4-triazole derivative in the ligand, and the HOMO level is-. Use with a deep compound of 5.4 eV or less facilitates the transfer of charge, leading to further improvements in luminous efficiency and drive voltage.

Moreover, the manufacturing method of the organic electroluminescent element of this invention is a manufacturing method of the organic electroluminescent element which manufactures the said organic electroluminescent element, The structure represented by the said General formula (1) among the said organic layers The layer containing the compound which has is formed by the wet process, It is characterized by the above-mentioned. As a result, an organic electroluminescent device having a light emission ratio of a component having a longer wavelength than the maximum light emission wavelength, high light emission efficiency, low driving voltage and long light emission lifetime, small voltage rise during driving, and excellent stability over time can be produced. Can be.

In addition, the display device and the lighting device of the present invention are characterized by including the organic electroluminescent element.

Moreover, the organic electroluminescent element material of this invention is characterized by containing the compound which has a structure represented by the said General formula (1). By using this organic electroluminescent element material, the emission ratio of components having a longer wavelength than the maximum luminescence maximum wavelength is high, high luminous efficiency, low driving voltage, long luminous lifetime, small voltage rise during driving, and excellent organic stability over time. An electroluminescent element can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, the form, aspect for implementing this invention, its component, and this invention are demonstrated in detail. In addition, in this application, "-" showing the numerical range is used by the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

<< summary of organic electroluminescent element >>

The organic electroluminescent device of the present invention is an organic electroluminescent device having an organic layer sandwiched by at least one pair of anodes and cathodes, the organic layer including at least one layer including a light emitting layer, and among the organic layers At least one layer contains the compound which has a structure represented by General formula (1), It is characterized by the above-mentioned. General formula (1) is mentioned later.

Although the following structures are mentioned as a typical element structure in the organic electroluminescent element of this invention, It is not limited to these.

(1) anode / light emitting layer / cathode

(2) anode / light emitting layer / electron transporting layer / cathode

(3) anode / hole transport layer / light emitting layer / cathode

(4) anode / hole transport layer / light emitting layer / electron transport layer / cathode

(5) Anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(6) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode

(7) Anode / hole injection layer / hole transport layer / (electron blocking layer /) light emitting layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode

Although the structure of (7) is used preferably in the above, it is not limited to this.

The light emitting layer which concerns on this invention is comprised from single layer or multiple layers, and when comprised by multiple layers, you may form a non-light emitting intermediate layer between each light emitting layer.

If necessary, a hole blocking layer (also called a hole barrier layer) or an electron injection layer (also called a cathode buffer layer) may be provided between the light emitting layer and the cathode, or an electron blocking layer (also called an electron barrier layer) between the light emitting layer and the anode. A hole injection layer (also called an anode buffer layer) may be provided.

The electron transporting layer used in the present invention is a layer having a function of transporting electrons. In a broad sense, the electron injection layer and the hole blocking layer are also included in the electron transporting layer. The electron transport layer may be composed of a plurality of layers.

The hole transport layer used in the present invention is a layer having a function of transporting holes, and in a broad sense, the hole injection layer and the electron blocking layer are also included in the hole transport layer. The hole transport layer may be composed of a plurality of layers.

In the said typical element structure, the layer except an anode and a cathode is made into an "organic layer."

(Tandem structure)

The organic EL device of the present invention may be a device having a so-called tandem structure in which a plurality of light emitting units including at least one light emitting layer are stacked.

As a typical element structure of a tandem structure, the following structures are mentioned, for example.

Anode / first light emitting unit / second light emitting unit / third light emitting unit / cathode

Anode / first light emitting unit / middle layer / second light emitting unit / middle layer / third light emitting unit / cathode

The first light emitting unit, the second light emitting unit, and the third light emitting unit may all be the same or different. In addition, two light emitting units may be the same and one remaining may be different.

The third light emitting unit may not be provided, and on the other hand, a light emitting unit or an intermediate layer may be further provided between the third light emitting unit and the cathode.

As in the configuration example, the plurality of light emitting units may be directly stacked or may be stacked via an intermediate layer.

The intermediate layer is generally called an intermediate electrode, an intermediate conductive layer, a charge generating layer, an electron withdrawing layer, a connection layer, or an intermediate insulating layer, and has a function of supplying electrons to adjacent layers on the anode side and holes to adjacent layers on the cathode side. If it is a layer, a well-known material and a structure can be used.

Examples of the material used for the intermediate layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO ₂ , TiN, ZrN, HfN, TiO _x , VO _x , CuI, InN, GaN, CuAlO ₂ , Conductive inorganic compound layers such as CuGaO ₂ , SrCu ₂ O ₂ , LaB ₆ , RuO ₂ , Al, two-layer films such as Au / Bi ₂ O ₃ , SnO ₂ / Ag / SnO ₂ , ZnO / Ag / ZnO, Bi _{2 O 3 / Au / Bi 2} O 3, TiO 2 / TiN / TiO 2, TiO 2 / ZrN / TiO 2 , etc. of the multilayer film, and a conductive organic material, metal phthalocyanines such as fullerene acids, oligothiophene, such as C _60, Although conductive organic compound layers, such as a metal free phthalocyanine, metal porphyrins, and a metal porphyrin, etc. are mentioned, this invention is not limited to these.

As a preferable structure in a light emitting unit, although the anode and cathode were removed from the structure of (1)-(7) illustrated by the said typical element structure, for example, this invention is not limited to these.

As a specific example of a tandem type organic electroluminescent element, For example, US patent 6337492 specification, US patent 7420203 specification, US patent 7474723 specification, US patent 6872472 specification, US patent 6107734 specification, US patent application 6337492, International Publication 2005/009087, Japanese Patent Laid-Open No. 2006-228712, Japanese Patent Laid-Open No. 2006-24791, Japanese Patent Laid-Open No. 2006-49393, Japanese Patent Laid-Open No. 2006-49394 Japanese Patent Laid-Open No. 2006-49396, Japanese Patent Laid-Open No. 2011-96679, Japanese Patent Laid-Open No. 2005-340187, Japanese Patent No. 4711424, Japanese Patent No. 3496681, Japanese Patent No. 3884564 Japanese Patent Laid-Open No. 4213169, Japanese Patent Laid-Open No. 2010-192719, Japanese Patent Laid-Open No. 2009-076929, Japanese Patent Laid-Open No. 2008-078414, Japanese Patent Laid-Open No. 2007-059848, Japanese patent Although the element structure, structural material, etc. which were described in Unexamined-Japanese-Patent No. 2003-272860, Unexamined-Japanese-Patent No. 2003-045676, international publication 2005/094130, etc. are mentioned, This invention is not limited to these.

Each layer which comprises the organic electroluminescent element of this invention is demonstrated.

`` Light emitting layer ''

The light emitting layer according to the present invention is a layer which emits light when an exciton generated by recombination of electrons and holes injected from a cathode or an electron transporting layer or an anode or a hole transporting layer is deactivated, and the light emitting portion is a light emitting layer and an adjacent layer even if the light emitting layer is in the layer of the light emitting layer. The interface of may be sufficient.

Although the sum total of the layer thickness of a light emitting layer does not have a restriction | limiting in particular, From a viewpoint of the homogeneity of a film | membrane and the prevention of unnecessary high voltage at the time of light emission, and the improvement of the stability of light emission color with respect to a drive current, Preferably it is the range of 2 nm-5 micrometers. It is adjusted to, more preferably in the range of 2 to 200 nm, particularly preferably in the range of 5 to 100 nm.

In the preparation of the light emitting layer, a light emitting dopant or a host compound described later is, for example, vacuum evaporation method or wet method (also called wet process, for example, spin coating method, casting method, die coating method, blade coating method, roll coating method, ink jet method). Film forming method, printing method, spray coating method, curtain coating method, LB method (such as Langmuir Blodgett method), and the like. Preferably, the light emitting layer is a layer formed through a wet process. By forming a layer by a wet process, the damage of a light emitting layer by heat can be reduced compared with the vacuum vapor deposition method.

The light emitting layer of the organic EL device of the present invention contains a light emitting dopant and a host compound, and at least one light emitting dopant is a phosphorescent organic metal complex having a structure represented by the general formula (1) described above, preferably a general formula It is a phosphorescent organic metal complex which has a structure represented by any of (5)-(10).

Moreover, you may use together the compound etc. which are described in the following patent publications for the light emitting layer which concerns on this invention.

For example, International Publication No. 00/70655, Japanese Patent Laid-Open No. 2002-280178, Japanese Patent Laid-Open No. 2001-181616, Japanese Patent Laid-Open No. 2002-280179, Japanese Patent Laid-Open No. 2001-181617 Japanese Patent Laid-Open No. 2002-280180, Japanese Patent Laid-Open No. 2001-247859, Japanese Patent Laid-Open No. 2002-299060, Japanese Patent Laid-Open No. 2001-313178, Japanese Patent Laid-Open No. 2002-302671 Japanese Patent Laid-Open No. 2001-345183, Japanese Patent Laid-Open No. 2002-324679, International Publication No. 02/15645, Japanese Patent Laid-Open No. 2002-332291, Japanese Patent Laid-Open No. 2002-50484, Japanese Patent Laid-Open No. 2002-332292, Japanese Patent Laid-Open No. 2002-83684, Japanese Patent Laid-Open No. 2002-540572, Japanese Patent Laid-Open No. 2002-117978, Japanese Patent Laid-Open No. 2002-338588, Japanese Patent Laid-Open No. 2002-170684, Japanese Patent Laid-Open No. 2002-35296 0, International Publication No. 01/93642, Japanese Patent Publication No. 2002-50483, Japanese Patent Publication No. 2002-100476, Japanese Patent Publication No. 2002-173674, Japanese Patent Publication No. 2002-359082 Japanese Patent Laid-Open No. 2002-175884, Japanese Patent Laid-Open No. 2002-363552, Japanese Patent Laid-Open No. 2002-184582, Japanese Patent Laid-Open No. 2003-7469, Japanese Patent Laid-Open No. 2002-525808 Japanese Patent Publication No. 2003-7471, Japanese Patent Publication No. 2002-525833, Japanese Patent Publication No. 2003-31366, Japanese Patent Publication No. 2002-226495, Japanese Patent Publication No. 2002-234894 Japanese Patent Laid-Open No. 2002-235076, Japanese Patent Laid-Open No. 2002-241751, Japanese Patent Laid-Open No. 2001-319779, Japanese Patent Laid-Open No. 2001-319780, Japanese Patent Laid-Open No. 2002-62824 Japanese Unexamined Patent Application Publication No. 2002-100474 2002-203679, Japanese Patent Laid-Open No. 2002-343572, Japanese Patent Laid-Open No. 2002-203678, and the like.

Next, while describing the compound contained in an organic layer, each layer is demonstrated.

(1) light emitting dopant

As the light emitting dopant, a fluorescent dopant (also called a fluorescent compound) and a phosphorescent dopant (also called a phosphorescent dopant, a phosphorescent compound, a phosphorescent compound, etc.) can be used.

(1.1) phosphorescent dopants

The phosphorescent dopant according to the present invention is a compound in which luminescence from an excitation triplet is observed, specifically, a compound which phosphorescence emits at room temperature (25 ° C), and is defined as a compound having a phosphorescent quantum yield of 0.01 or more at 25 ° C. Phosphorescent quantum yield is at least 0.1.

The phosphorescent quantum yield can be measured by the method described in page 398 (Maruzen, 1992 edition) of Spectrum II of Fourth Edition Experimental Chemistry Course 7. Although the phosphorescent quantum yield in a solution can be measured using various solvents, the phosphorescence dopant which concerns on this invention should just achieve the said phosphorescence quantum yield (0.01 or more) in any solvent.

There are two types of light emission of the phosphorescent dopant, one of which causes recombination of carriers on the host compound to which the carrier is transported to generate an excited state of the host compound, and the light emission from the phosphorescent dopant by transferring this energy to the phosphorescent dopant. Obtaining energy is mobile. The other is a carrier trap type in which the phosphorescent dopant becomes a carrier trap, and carrier recombination occurs on the phosphorescent dopant, so that light emission from the phosphorescent dopant is obtained. In all cases, it is a condition that the energy of the excited state of a phosphorescent dopant is lower than the energy of the excited state of a host compound.

As a phosphorescent dopant in embodiment of this invention, it is preferable to use the phosphorescent organic metal complex which has a structure represented by General formula (1) demonstrated below.

By using a phosphorescent organic metal complex having a structure represented by the general formula (1) as a phosphorescent dopant, long-wave emission components can be suppressed while maintaining a short wavelength, and high emission luminance, low driving voltage, and emission lifetime Long life can be achieved at the same time. In addition, the organic EL device fabricated using the phosphorescent dopant of the present invention has a small increase in voltage at the time of driving and is improved in terms of stability over time.

(1.1.1) A compound having a structure represented by General Formula (1)

In General formula (1), R <_1> -R <_4> is respectively independently a hydrogen atom and an alkyl group (for example, a methyl group, an ethyl group, a propyl group, isopropyl group, (t) butyl group, a pentyl group, a hexyl group, an jade) Tyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, benzyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, allyl Groups), alkynyl groups (e.g., propargyl groups, etc.), aromatic hydrocarbon groups (also called aryl groups, for example, phenyl groups, p-chlorophenyl groups, mesityl groups, tolyl groups, xylyl groups, naphthyl groups, Trill group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc., heterocyclic group (for example, epoxy ring, aziridine ring, thiirane ring, oxe) Bullet ring, azetidine ring, thiethane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, Sazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε-caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, Morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine ring, thiomorpholine 1,1-dioxide ring , Pyranose ring, diazabicyclo [2,2,2] -octane ring, etc.), aromatic heterocyclic group (pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, Pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzooxa Zolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, car bar Zolyl group, carbolinyl group, diazacarbazolyl group (showing that one of the carbon atoms constituting the carboline ring of the carbolinyl group is substituted with a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl group , Quinazolinyl group, phthalazinyl group, etc.), halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc., cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, naph Methyloxy group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, For example, a cyclopentylthio group, a cyclohexylthio group, etc.), an arylthio group (for example , Phenylthio group, naphthylthio group, etc., alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyl Oxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylamino Sulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureide group (for example, methyl uraide group, ethyl uraide group, pentyl woo) Rade group, cyclohexyl uraide group, octyl uraide group, dodecyl uraide group, phenyl uraide group, naphthyl uraide group, 2-pyridylamino uraide group, etc.), acyl group ( For example, an acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (such as) For example, an acetyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an octylcarbonyloxy group, a dodecylcarbonyloxy group, a phenylcarbonyloxy group, etc.), an amide group (for example, methyl carbon) Carbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbon Carbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl , Dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc. ), Sulfinyl (for example, methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyri) Dimethyl sulfonyl group or arylsulfonyl group (for example, methyl sulfonyl group, ethyl sulfonyl group, butyl sulfonyl group, cyclohexyl sulfonyl group, 2-ethylhexyl sulfonyl group, dodecyl sulfonyl group, phenyl sulfonyl group) , Naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentyl group) No group, 2-ethylhexylamino group, dodecylamino group, anilino group, diarylamino group (for example, diphenylamino group, dinaphthylamino group, phenylnaphthylamino group, etc.), naphthylamino group, 2-pyridylamino group, etc. ), Nitro group, cyano group, hydroxy group, mercapto group, alkylsilyl group or arylsilyl group (e.g. trimethylsilyl group, triethylsilyl group, (t) butyldimethylsilyl group, triisopropylsilyl group, (t ) Butyldiphenylsilyl group, triphenylsilyl group, trinaphthylsilyl group, 2-pyridylsilyl group, etc.), alkyl phosphino group or aryl phosphino group (dimethyl phosphino group, diethyl phosphino group, dicyclo Hexylphosphino group, methylphenylphosphino group, diphenylphosphino group, dinaphthylphosphino group, di (2-pyridyl) phosphino group), alkylphosphoryl group or arylphosphoryl group (dimethylphosphoryl group, Diethylphosphoryl group, dicyclohexylphosphoryl group, methylphenylphosphoryl group, Phenylphosphoryl group, dinaphthylphosphoryl group, di (2-pyridyl) phosphoryl group), alkylthiophosphoryl group or arylthiophosphoryl group (dimethylthiophosphoryl group, diethylthiophosphoryl group, dish) Clohexylthiophosphoryl group, methylphenylthiophosphoryl group, diphenylthiophosphoryl group, dinaphthylthiophosphoryl group, di (2-pyridyl) thiophosphoryl group). Here, groups other than the said hydrogen atom are represented by a substituent. In addition, these substituents may be further substituted by the said substituent, and they may be condensed with each other and may form the ring further.

In addition, the specific example in parentheses in these substituents is not limited to these. In addition, the parentheses in the alkyl group, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfinyl group, sulfonyl group, nitro group, cyano group, hydroxy group, and mercapto group in the substituent described above. About the specific example within, the alkyl group, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfinyl group, sulfonyl group, nitro group, cyano group, and hydroxy group of R of General formula (1) The same applies to the mercapto group. In addition, about the specific example in parentheses in the aromatic hydrocarbon group or aromatic heterocyclic group in the said substituent, it is the same also in the aromatic hydrocarbon group or aromatic heterocyclic group of Ar of General formula (1).

When R <_1> -R <_4> represents the said substituent, any of an alkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an aryloxy group, an arylthio group, an amino group, and a cyano group is preferable, and especially an aromatic hydrocarbon Any of a group, an aromatic heterocyclic group, a halogen atom and a cyano group is preferable, and a halogen atom or cyano group is particularly preferable.

In general formula (1), R is an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxyl group, and a mercapto group Which group is selected. In addition, these groups may be further substituted by the said substituent. R is preferably any of an alkyl group, a halogen atom, or a cyano group, and is particularly preferably an alkyl group or a cyano group from the viewpoint of more effectively suppressing light emission of a component having a longer wavelength than the maximal emission wavelength, and is an alkyl group having 1 to 6 carbon atoms. Is particularly preferred.

In General formula (1), Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. In addition, these groups may be further substituted by the said substituent, and they may be condensed with each other and may form the ring further. It is preferable that Ar is substituted by the said substituent, Especially, it is preferable to be substituted by any of an alkyl group, a cycloalkyl group, a halogen atom, an aromatic hydrocarbon group, a heterocyclic group, and an aromatic heterocyclic group, Especially an alkyl group, an aromatic hydrocarbon group, or It is preferable that it is substituted by the aromatic heterocyclic group. Moreover, the bond with the 1H-1,2,4-triazole ring of the ring represented by (Ar) by which the ortho position is substituted with respect to the bonding position with the 1H-1,2,4-triazole ring of General formula (1) The substituent having a substituent at a position adjacent to the position is preferable in terms of shortening the emission wavelength, and particularly preferably substituted with an alkyl group.

In General formula (1), X <_1> -L <_1> -X <_2> represents a bidentate ligand, X <_1> and X <_2> respectively independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ .

Specific examples of the bidentate ligand represented by X ₁ -L ₁ -X ₂ include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, Although picolinic acid etc. are mentioned, It is not limited to these. As a bidentate ligand represented by X <_1> -L <_1> -X <_2> , it is preferable that it is phenylpyrazole or phenyltriazole, and it is especially preferable that it is phenyltriazole.

In General formula (1), m represents the integer of 1-3, n represents the integer of 0-2, m + n is 3. It is preferable that n is 0 or 1, and it is preferable that it is 0 especially from a viewpoint which suppresses the light emission of the long wave component more effectively than the light emission maximum wavelength.

In General formula (1), at least 2 of adjacent R <_1> -R <_4> is condensed and represents any structure of General formula (2)-(4).

In General Formulas (2) to (4), Y ₁ to Y ₄ each independently represent O, S or N-R ', and Y ₅ or Y ₆ represents CR ″ or N. Y ₁ or Y ₄ Is particularly preferably N—R ′, preferably Y ₂ or Y ₃ is O or N—R ′, particularly preferably N—R ′. Y ₅ is preferably CR ″, and Y ₆ Is preferably N.

In General Formulas (2) to (4), R 'represents any group selected from an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, and an aromatic heterocyclic group. In addition, these groups may be further substituted by the said substituent, and they may be condensed with each other and may form the ring further. R 'is preferably any group selected from an aromatic hydrocarbon group, a heterocyclic group and an aromatic heterocyclic group, and particularly preferably an aromatic hydrocarbon group or an aromatic heterocyclic group.

In General Formulas (2) to (4), R ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, a cyano group, an arylsilyl group, and an arylphosphoryl group Moreover, these groups may be further substituted by the said substituent, and they may be condensed with each other and may form the further ring. R "is chosen from a hydrogen atom, an aromatic hydrocarbon group, and an aromatic heterocyclic group. It is preferable that it is either group.

In General Formulas (2) to (4), Z ₁ to Z ₈ each independently represent C-Rx or N, and a plurality of Rx may be the same or different, respectively. It is preferable that Z <_1> -Z <_8> is C-Rx. A plurality of Rx's each independently represent a group equivalent to R ₁ to R ₄ in General Formula (1). In addition, these groups may be further substituted by the said substituent, and they may be condensed with each other and may form the ring further. In the case where at least one of the plurality of Rx represents the substituent, Rx is preferably any group selected from alkyl group, aromatic hydrocarbon group, heterocyclic group, aromatic heterocyclic group, halogen atom, amino group and cyano group, especially alkyl group, aromatic Any group selected from a hydrocarbon group, an aromatic heterocyclic group, a halogen atom and a cyano group is preferable.

In General Formulas (2) to (4), * represents a bonding position with a structure represented by General Formula (1).

In addition, the compound which has a structure represented by said General formula (1) may be contained in organic layers other than a light emitting layer.

(1.1.2) A compound having a structure represented by general formulas (5) to (10)

It is preferable that the structure represented by General formula (1) is a structure represented by either of following General formulas (5)-(10).

In General Formulas (5) to (10), R, Ar, R ₁ to R ₄ , Y ₁ , Z ₁ to Z ₄ , X ₁ , X ₂ , L ₁ , m, and n are the general formulas (1) And (2) have the same meaning as R, Ar, R ₁ to R ₄ , Y ₁ , Z ₁ to Z ₄ , X ₁ , X ₂ , L ₁ , m and n.

(1.1.3) Embodiments

Hereinafter, although the specific example of the compound which has a structure represented by General formula (1) which concerns on this invention is shown, it is not limited to these.

(1.1.4) Synthesis Example

Although the synthesis example of the compound which has a structure represented by General formula (1)-(10) below is given and demonstrated the said exemplary compound 3-3 as an example, this invention is not limited to this.

Exemplary compound 3-3 can be synthesized according to the following scheme.

Into a flask under nitrogen stream, 5.0 g (9.60 mmol) of intermediate 1, 3.39 g (9.60 mmol) of iridium chloride, 40 mL of 2-ethoxyethanol, and 10 mL of water were added thereto, and the mixture was heated and stirred at 100 ° C. for 4 hours. The precipitated crystals were filtered out, and the filtered crystals were washed with methanol to obtain 11.5 g of intermediate 2.

Into a flask under nitrogen stream, 4.73 g (9.07 mmol) of intermediate 1, 11.5 g (4.54 mmol) of intermediate 2, 2.51 g (11.4 mmol) of trifluoroacetic acid and 230 mL of phenyl acetate were added and 9 hours at 180 ° C. It stirred by heating. The reaction solution was allowed to cool to room temperature, and then concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography to obtain 1.27 g (yield 8%) of Exemplary Compound 3-3. The structure of Exemplary Compound 3-3 was confirmed by mass spectrum and ¹ H-NMR. In addition, what sublimed and refine | purified this compound was used for preparation of the organic electroluminescent element mentioned later.

Other compounds of the present invention can also be synthesized in good yields by using appropriate raw materials and reactions in the same manner as in the above synthesis examples.

(1.2) Fluorescent Dopant

Examples of fluorescent dopants (hereinafter also referred to as fluorescent compounds) include coumarin pigments, pyran pigments, cyanine pigments, croconium pigments, squarylium pigments, oxobenzanthracene pigments, fluorescein pigments, rhodamine pigments, and pyryls. And a compound having a high fluorescence quantum yield represented by a laser pigment, such as a cerium dye, a perylene dye, a stilbene dye, a polythiophene dye, or a rare earth complex system phosphor.

In recent years, light emitting dopants using delayed fluorescence have also been developed, and these may be used.

As a specific example of the luminescent dopant using delayed fluorescence, although the compound described in Unexamined-Japanese-Patent No. 2011/156793, 2011-213643, 2010-93181, etc. is mentioned, this invention is mentioned, for example. Is not limited to these.

(1.3) Use with a conventionally known light emitting dopant

The light emitting dopant according to the present invention may be used in combination of a plurality of compounds, or may be used in combination of phosphorescent dopants having different structures, or in combination of phosphorescent dopants and fluorescent dopants. As a phosphorescent dopant and a fluorescent dopant to be used together, a well-known thing can be used.

(2) host compounds

In the present invention, among the compounds contained in the light emitting layer, the host compound (hereinafter also referred to as a light emitting host) has a mass ratio of 20% or more in the layer, and a phosphorescent quantum yield of phosphorescence emission at room temperature (25 ° C) of 0.1. It is defined as a compound that is less than. Preferably the phosphorescent quantum yield is less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more in the compound contained in a light emitting layer.

There is no restriction | limiting in particular as a light emitting host which can be used for this invention, The compound conventionally used by organic electroluminescent element can be used. Typically, those having basic skeletons such as carbazole derivatives, triarylamine derivatives, aromatic derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives and oligoarylene compounds, or carboline derivatives or diazacarbazole derivatives Here, a diazacarbazole derivative shows that at least 1 carbon atom of the hydrocarbon ring which comprises the carboline ring of a carboline derivative is substituted by the nitrogen atom, etc. are mentioned.

As a known light emitting host which can be used in the present invention, a compound having hole transporting ability and electron transporting ability, preventing long wavelength emission and further having a high Tg (glass transition temperature) is preferable.

In addition, in this invention, a conventionally well-known light emitting host may be used independently, or may be used in combination of multiple types. By using plural kinds of light emitting hosts, it is possible to adjust the movement of electric charges and to increase the efficiency of the organic EL element. Further, by using plural kinds of the metal complex of the present invention and / or a conventionally known compound used as the phosphorescent dopant, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

The light emitting host used in the present invention may be a low molecular compound or a high molecular compound having a repeating unit, or may be a low molecular compound (polymerizable light emitting host) having a polymerizable group such as a vinyl group or an epoxy group. You may use multiple types.

As a specific example of a known light-emitting host, Unexamined-Japanese-Patent No. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786 No. 2002-8860, No. 2002-334787, No. 2002-15871, No. 2002-334788, No. 2002-43056, No. 2002-334789, No. 2002-75645 Publications 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227 No. 2002-231453, No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183, The compound described in the literature of 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002-308837, etc. are mentioned.

In addition, as mentioned above, since the compound which has a structure represented by General formula (1) which concerns on this invention has a deep HOMO level, it is preferable to use that whose HOMO level is -5.4 eV or less as a host compound. As a result, the movement of charges becomes smooth, which leads to further improvement in luminous efficiency and driving voltage.

Next, an injection layer, a blocking layer, an electron transporting layer, a hole transporting layer, etc. which are preferably used as a constituent layer of the organic EL device of the present invention will be described.

<< electron transport layer >>

In the present invention, the electron transporting layer may include a material having a function of transporting electrons, and may have a function of transferring electrons injected from the cathode to the light emitting layer.

Although there is no restriction | limiting in particular about the total layer thickness of the electron carrying layer used for this invention, Usually, it is the range of 2 nm-5 micrometers, More preferably, it is 2-500 nm, More preferably, it is 5-200 nm.

In the organic EL device, when light generated in the light emitting layer is taken out from the electrode, light directly extracted from the light emitting layer and light taken out after being reflected by the electrode that is located in the light extracting electrode and the electrode positioned on the counter electrode cause interference. It is known. In the case where light is reflected by the cathode, it is possible to efficiently use this interference effect by appropriately adjusting the layer thickness of the electron transporting layer between several nm and several μm.

On the other hand, when the layer thickness of an electron carrying layer becomes thick, since voltage rises easily, especially when a layer thickness is thick, it is preferable that the electron mobility of an electron carrying layer is ^10-5 cm <^2> / Vs or more.

As a material (henceforth an electron transport material) used for an electron carrying layer, what is necessary is just to have any of electron injection property, transportability, and hole barrier property, and it can select and use arbitrary from a conventionally well-known compound.

For example, a nitrogen-containing aromatic heterocyclic derivative (carbazole derivative, azacarbazole derivative (in which at least one carbon atom constituting the carbazole ring is substituted with a nitrogen atom), pyridine derivative, pyrimidine derivative, pyrazine derivative, Pyridazine derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimi Diazole derivatives, benzoxazole derivatives, benzthiazole derivatives, and the like), dibenzofuran derivatives, dibenzothiophene derivatives, silol derivatives, aromatic hydrocarbon ring derivatives (naphthalene derivatives, anthracene derivatives, triphenylene and the like), and the like. .

Further, metal complexes having a quinolinol skeleton or a dibenzo quinolinol skeleton in the ligand, for example tris (8-quinolinol) aluminum (Alq3), tris (5,7-dichloro-8-quinolinol) Aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis ( 8-quinolinol) zinc (Znq) and the like, and metal complexes in which the center metal of these metal complexes are substituted with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as the electron transporting material.

In addition, metal free or metal phthalocyanine or those whose terminal is substituted by the alkyl group, sulfonic acid group, etc. can also be used suitably as an electron carrying material. In addition, distyrylpyrazine derivatives can also be used as the electron transporting material, and inorganic semiconductors such as n-Si and n-SiC can also be used as the electron transporting material in the same manner as the hole injection layer and the hole transporting layer.

Moreover, the polymeric material which introduce | transduced these materials into the polymer chain, or made these materials the main chain of a polymer can also be used.

In the electron transporting layer used in the present invention, the electron transporting layer may be doped with a dope material as a guest material to form an electron transporting layer having a high n property (electron rich). Examples of the dope material include n-type dopants such as metal compounds such as metal complexes and metal halides. As a specific example of the electron carrying layer of such a structure, For example, Unexamined-Japanese-Patent No. 4-297076, 10-270172, Unexamined-Japanese-Patent No. 2000-196140, 2001-102175, J. Appl . And those described in Phys., 95, 5773 (2004) and the like.

Although the compound etc. which were described in the following documents are mentioned as a specific example of a well-known preferable electron transport material used for the organic electroluminescent element of this invention, This invention is not limited to these.

U.S. Pat.6528187, U.S.7230107, U.S. Patent Publication 2005/0025993, U.S. Patent Application Publication 2004/0036077, U.S. Patent Application Publication 2009/0115316, U.S. Patent Application Publication 2009/0101870, US Patent Application Publication 2009/0179554, International Publication 2003/060956, International Publication 2008/132085, Appl. Phys. Lett., 75, 4 (1999), Appl. Phys. Lett., 79, 449 (2001), Appl. Phys. Lett., 81, 162 (2002), Appl. Phys. Lett., 81, 162 (2002), Appl. Phys. Lett., 79, 156 (2001), US Patent No. 7764293, US Patent Application Publication No. 2009/030202, International Publication 2004/080975, International Publication 2004/063159, International Publication 2005/085387 International Publication No. 2006/067931, International Publication No. 2007/086552, International Publication No. 2008/114690, International Publication No. 2009/069442, International Publication No. 2009/066779, International Publication No. 2009/054253, International Publication No. 2011/086935, International Publication No. 2010/150593, International Publication No. 2010/047707, European Japanese Patent No. 2311826, Japanese Patent Publication No. 2010-251675, Japanese Patent Publication No. 2009-209133 Japanese Patent Laid-Open No. 2009-124114, Japanese Patent Laid-Open No. 2008-277810, Japanese Patent Laid-Open No. 2006-156445, Japanese Patent Laid-Open No. 2005-340122, Japanese Patent Laid-Open No. 2003-45662 Japanese Patent Laid-Open No. 2003-31367, Japanese Patent Laid-Open No. 2003-282270, International Publication 20 12/115034 and the like.

More preferred electron transport materials in the present invention include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives and benzimidazole derivatives. Can be mentioned.

The electron transporting material may be used alone, or may be used in combination.

<< hole blocking layer >>

The hole blocking layer is a layer having a function of an electron transporting layer in a broad sense, and preferably includes a material having a function of transporting electrons and a small ability to transport holes, and blocking holes while transporting electrons. The probability of recombination of holes can be improved. In addition, the structure of the above-mentioned electron transport layer can be used as a hole-blocking layer used for this invention as needed. It is preferable that the hole blocking layer provided in the organic EL element of the present invention is provided adjacent to the cathode side of the light emitting layer.

As layer thickness of the hole blocking layer used for this invention, Preferably it is the range of 3-100 nm, More preferably, it is the range of 5-30 nm.

As a material used for a hole blocking layer, the material used for the said electron carrying layer is used preferably, and the material used as a host compound mentioned above is also used preferably for a hole blocking layer.

<< electron injection layer >>

The electron injection layer (also referred to as the "cathode buffer layer") used in the present invention is a layer provided between the cathode and the light emitting layer for lowering the driving voltage and improving the luminance of light emission, and the "organic EL element and its industrialization front line (Nov. 1998) (Published on November 30) by Part II, "Electrode Materials" (123 to 166).

In this invention, an electron injection layer may be provided as needed and may exist between a cathode and a light emitting layer or between a cathode and an electron carrying layer as mentioned above.

It is preferable that an electron injection layer is an extremely thin film, and although it changes with a raw material, the layer thickness is preferable in the range of 0.1-5 nm. Moreover, the nonuniform film | membrane in which a component material exists intermittently may be sufficient.

The details of the electron injection layer are also described in Japanese Patent Laid-Open Nos. 6-325871, 9-17574, 10-74586, and the like. As a specific example of the material preferably used for the electron injection layer, strontium Metals such as aluminum and aluminum, alkali metal compounds represented by lithium fluoride, sodium fluoride, potassium fluoride and the like, alkaline earth metal compounds represented by magnesium fluoride and calcium fluoride, metal oxides represented by aluminum oxide, and lithium 8-hydroxy The metal complex represented by quinolate (Liq) etc. are mentioned. It is also possible to use the electron transport material described above.

In addition, the material used for the said electron injection layer may be used independently, and may be used in combination of multiple types.

Hole Transport Layer

In the present invention, the hole transport layer includes a material having a function of transporting holes, and may have a function of transferring holes injected from the anode to the light emitting layer.

Although there is no restriction | limiting in particular about the total layer thickness of the positive hole transport layer used for this invention, Usually, it is the range of 5 nm-5 micrometers, More preferably, it is 2-500 nm, More preferably, it is 5-200 nm.

As a material (henceforth a hole transport material) used for a hole transport layer, what is necessary is just to have any of hole injection property, transport property, and electron barrier property, and it can select and use arbitrary from a conventionally well-known compound.

For example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyaryls Main chain or side chain of alkane derivative, triarylamine derivative, carbazole derivative, indolocarbazole derivative, isoindole derivative, acene derivative such as anthracene or naphthalene, fluorene derivative, fluorenone derivative and polyvinylcarbazole, aromatic amine And polymeric materials or oligomers, polysilanes, conductive polymers or oligomers (for example, PEDOT / PSS, aniline copolymers, polyanilines, polythiophenes, etc.) introduced into the polymer.

Examples of the triarylamine derivative include benzidine type represented by α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), starburst type represented by MTDATA, and tri The compound which has fluorene and anthracene in an arylamine connection core part, etc. are mentioned.

In addition, hexaazatriphenylene derivatives described in JP-A-2003-519432, JP-A-2006-135145, and the like can also be used as hole transport materials.

In addition, a highly p-type hole transport layer doped with impurities may be used. Examples include Japanese Patent Laid-Open No. 4-297076, Japanese Patent Laid-Open No. 2000-196140, and Japanese Patent Laid-Open No. 2001-102175, J. Appl. Phys., 95, 5773 (2004) etc. are mentioned.

In addition, Japanese Patent Laid-Open No. 11-251067, J. Huang et. al. So-called p-type hole transport materials and inorganic compounds such as p-Si and p-SiC described in Appl. Phys. Lett., 80 (2002), p. 139 may also be used. . Moreover, the orthometallic organometallic complex which has Ir and Pt in the center metal represented by Ir (ppy) ₃ is also used preferably.

Although the above can be used as a hole transport material, the polymer material or oligomer which introduce | transduced the triarylamine derivative, the carbazole derivative, the indolocarbazole derivative, the azatriphenylene derivative, the organometallic complex, and the aromatic amine in the main chain or the side chain. Etc. are used preferably.

As a specific example of a well-known preferable hole transport material used for the organic electroluminescent element of this invention, although the compound etc. which were described in the following documents are mentioned besides the literature enumerated above, this invention is not limited to these.

For example, Appl. Phys. Lett., 69, 2160 (1996), J. Lumin., 72-74, 985 (1997), Appl. Phys. Lett., 78, 673 (2001), Appl. Phys. Lett., 90, 183503 (2007), Appl. Phys. Lett., 90, 183503 (2007), Appl. Phys. Lett., 51, 913 (1987), Synth. Met., 87, 171 (1997), Synth. Met., 91, 209 (1997), Synth. Met., 111, 421 (2000), SID Symposium Digest, 37, 923 (2006), J. Mater. Chem., 3, 319 (1993), Adv. Mater., 6, 677 (1994), Chem. Mater., 15, 3148 (2003), US Patent Application Publication No. 2003/0162053, US Patent Application Publication No. 2002/0158242, US Patent Application Publication No. 2006/0240279, US Patent Application Publication No. 2008 / 0220265 Specification, US Patent No. 5051569, International Publication No. 2007/002683, International Publication No. 2009/018009, European Japanese Patent No. 650955 Specification, US Patent Application Publication No. 2008/0124572 Specification, US Patent Application Publication US Patent Application Publication No. 2008/0106190, US Patent Application Publication No. 2008/0018221, International Publication 2012/115034, Japanese Patent Publication No. 2003-519432, Japanese Patent Publication US 2006-135145, US patent application Ser. No. 13/585981, and the like.

A hole transport material may be used independently and may be used in combination of multiple types.

Electronic blocking layer

The electron blocking layer is a layer having a function of a hole transporting layer in a broad sense, and preferably includes a material having a function of transporting holes and having a small ability to transport electrons, and blocking electrons while transporting holes. The probability of recombination of holes can be improved.

In addition, the structure of the above-mentioned hole transport layer can be used as an electron blocking layer used for this invention as needed.

It is preferable that the electron blocking layer provided in the organic electroluminescent element of this invention is provided adjacent to the anode side of a light emitting layer.

As layer thickness of the electron blocking layer used for this invention, Preferably it is the range of 3-100 nm, More preferably, it is the range of 5-30 nm.

As a material used for an electron blocking layer, the material used for the above-mentioned hole transport layer is used preferably, and the material used as a host compound mentioned above is also used preferably for an electron blocking layer.

<< hole injection layer >>

The hole injection layer (also referred to as the "anode buffer layer") used in the present invention is a layer provided between the anode and the light emitting layer for lowering the driving voltage and improving the luminance of light emission, and the "organic EL element and its industrialization front line (Nov. 1998) (Published on November 30) by Part II, "Electrode Materials" (123 to 166).

In the present invention, the hole injection layer may be provided as necessary, and may be present between the anode and the light emitting layer or the anode and the hole transport layer as described above.

The details of the hole injection layer are also described in Japanese Patent Application Laid-Open Nos. 9-45479, 9-260062, 8-288069, and the like. Examples of the material used for the hole injection layer include the above-mentioned materials. The material used for a positive hole transport layer, etc. are mentioned.

Among them, a phthalocyanine derivative represented by copper phthalocyanine, a hexaazatriphenylene derivative described in Japanese Patent Publication No. 2003-519432, Japanese Patent Laid-Open Publication No. 2006-135145, etc., a metal oxide represented by vanadium oxide, amorphous carbon Orthometallized complexes represented by a conductive polymer such as polyaniline (emeraldine) or polythiophene, a tris (2-phenylpyridine) iridium complex, and the like, and a triarylamine derivative are preferable.

The material used for the above-mentioned hole injection layer may be used independently, and may use it in combination of multiple types.

<< other addition compounds >>

The organic layer in this invention mentioned above may further contain the other additive compound. Examples of the additive compound include halogen elements such as bromine, iodine and chlorine, halogenated compounds, alkali metals such as Pd, Ca, and Na, alkaline earth metals, compounds, complexes, and salts of transition metals.

Although content of an addition compound can be arbitrarily determined, it is preferable that it is 1000 ppm or less with respect to the total mass% of the layer to contain, More preferably, it is 500 ppm or less, More preferably, it is 50 ppm or less.

However, it is not within this range depending on the purpose of improving the transportability of electrons and holes, or the purpose of facilitating energy transfer of excitons.

<< formation method of organic layer >>

The formation method of the organic layer (hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) used for this invention is demonstrated.

There is no restriction | limiting in particular in the formation method of the organic layer used for this invention, Although the formation method by a conventionally well-known example, for example, a vacuum deposition method, a wet method (also called a wet process), etc. can be used, It is preferable that an organic layer is a layer formed by the wet process. . That is, it is preferable to manufacture organic electroluminescent element by a wet process. By producing an organic EL element by a wet process, a homogeneous film (coating film) is easy to be obtained and an effect such that pinholes are hard to be produced can be exhibited. In addition, the film | membrane (coating film) here is a thing dried after application | coating by a wet process.

Examples of the wet method include spin coating method, cast method, ink jet method, printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, LB method (Langmuir-Blodgett method), and the like. A thin film is easy to be obtained, and from the viewpoint of high productivity, a method having high roll-to-roll aptitude such as a die coating method, a roll coating method, an inkjet method, and a spray coating method is preferable.

Examples of the liquid medium for dissolving or dispersing the organic EL material of the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene and mesh. Aromatic hydrocarbons, such as styrene and cyclohexylbenzene, aliphatic hydrocarbons, such as cyclohexane, decalin, and dodecane, organic solvents, such as DMF and DMSO, can be used.

Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

Moreover, you may apply the film forming method different for every layer. When the vapor deposition method is adopted for the film formation, the vapor deposition conditions are different depending on the kind of the compound to be used and the like, but in general, the boat heating temperature is 50 to 450 ° C., the vacuum degree is 10 ⁻⁶ to 10 ⁻² Pa, the deposition rate is 0.01 to 50 nm / second, It is preferable to select suitably in the range of substrate temperature -50-300 degreeC, layer thickness 0.1nm-5micrometer, Preferably 5-200nm.

Formation of the organic layer according to the present invention is preferably carried out from the hole injection layer to the cathode consistently in one vacuum, but may be taken out in the middle and subjected to another film forming method. In that case, it is preferable to perform work in a dry inert gas atmosphere.

"anode"

As the anode in the organic EL device, one having a large work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is preferably used. Specific examples of such electrode materials include metals such as Au, conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

Further, a transparent conductive film such as an amorphous IDIXO (In ₂ O ₃ -ZnO) may be used for making the material available.

As a method for forming the anode, a thin film may be formed by a method such as vapor deposition or sputtering using these electrode materials, and a pattern of a desired shape may be formed by a photolithography method, or when pattern precision is not required very much ( 100 micrometers or more), You may form a pattern through the mask of a desired shape at the time of vapor deposition or sputtering of the said electrode material.

In addition, when using the substance which can be apply | coated like an organic electroconductive compound, a wet film forming method, such as a printing system and a coating system, can also be used. When taking out light emission from this anode, it is preferable to make the transmittance | permeability larger than 10%, and the sheet resistance as an anode has preferable several hundred ohm / square or less.

The thickness of the anode varies depending on the material, but is usually selected in the range of 10 nm to 1 탆, preferably 10 to 200 nm.

"cathode"

As the cathode, one having a small work function (4 eV or less) of metal (called an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium / copper mixtures, magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, Indium, lithium / aluminum mixture, aluminum, rare earth metal and the like. Among them, in view of durability against electron injection property and oxidation, a mixture of an electron injection metal with a second metal having a higher work function value and a stable metal, for example, a magnesium / silver mixture, a magnesium / aluminum mixture, Magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable.

A cathode can be produced by forming a thin film of these electrode materials by methods, such as vapor deposition and sputtering. Further, the sheet resistance as the cathode is preferably several hundred? /? Or less, and the thickness is usually selected in the range of 10 nm to 5 mu m, preferably 50 to 200 nm.

In addition, in order to transmit the light emitted, if either one of the anode or the cathode of the organic EL element is transparent or semitransparent, the light emission luminance is improved, which is preferable.

In addition, after the metal is produced in the cathode with a thickness of 1 to 20 nm, a transparent or semitransparent cathode can be produced by fabricating the conductive transparent material listed in the description of the anode thereon, and by applying this, both of the anode and the cathode can be manufactured. An element having this permeability can be produced.

<< support board >>

As a support substrate (henceforth a base material, a board | substrate, a base material, a support body, etc.) which can be used for the organic electroluminescent element of this invention, there are no limitations in particular in kinds, such as glass and a plastic, and you may be transparent or opaque. When taking out light from the support substrate side, it is preferable that a support substrate is transparent. Glass, quartz, and a transparent resin film are mentioned as a transparent support substrate used preferably. Especially preferable support substrate is a resin film which can provide flexibility to organic electroluminescent element.

Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose acetate pro. Cellulose esters or derivatives thereof, such as cypionate (CAP), cellulose acetate phthalate, cellulose nitrate, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, Polymethylpentene, polyetherketone, polyimide, polyethersulfone (PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethyl methacrylate , Acrylic or polyarylates And cycloolefin-based resins such as Aton (trade name manufactured by JSR Corporation) or Apel (trade name Mitsui Chemicals, Inc.).

The inorganic film, the organic film, or a hybrid film of both thereof may be formed on the surface of the resin film, and water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2%) measured by the method according to JIS K 7129-1992 may be It is preferable that it is a gas barrier film of 1x10 <^-2> g / (m <^{2> *} 24h) or less, and also the oxygen permeability measured by the method based on JISK7126-1987 is 1x10 <^-3> mL / (m <^{2> *).} It is preferable that it is a high gas barrier film of 24 h * atm) or less and water vapor permeability of 1x10 <^-5> g / (m <^{2> *} 24h) or less.

As a material for forming the gas barrier film, a material having a function of suppressing intrusion, although it causes deterioration of elements such as moisture and oxygen, may be used, for example, silicon oxide, silicon dioxide, silicon nitride, or the like. Moreover, in order to improve the fragility of the said film | membrane, it is more preferable to have a laminated structure of these inorganic layers and the layer containing an organic material. Although there is no restriction | limiting in particular about the lamination order of an inorganic layer and an organic layer, It is preferable to laminate both alternately multiple times.

There is no restriction | limiting in particular about the formation method of a gas barrier film, For example, a vacuum vapor deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD method Although the laser CVD method, the thermal CVD method, the coating method, etc. can be used, it is especially preferable by the atmospheric plasma polymerization method described in Unexamined-Japanese-Patent No. 2004-68143.

As an opaque support substrate, metal plates, such as aluminum and stainless steel, a film, an opaque resin substrate, a ceramic substrate, etc. are mentioned, for example.

It is preferable that it is 1% or more, and, as for the external extraction quantum efficiency at room temperature of light emission of the organic electroluminescent element of this invention, it is more preferable if it is 5% or more.

Here, the external extraction quantum efficiency (%) is the number of electrons x100 passed to the photon number / organic EL element emitted to the outside of the organic EL element.

Moreover, even if it uses together color improvement filters, such as a color filter, you may use together the color conversion filter which converts into multicolor using the light emission color from organic electroluminescent element as a fluorescent substance.

<< sealing >>

As a sealing means used for sealing the organic electroluminescent element of this invention, the method of bonding a sealing member, an electrode, and a support substrate with an adhesive agent is mentioned, for example. As a sealing member, what is necessary is just to arrange | position so that the display area of an organic EL element may be covered, and a concave-plate shape or a flat plate shape may be sufficient as it. In addition, transparency and electrical insulation are not specifically limited.

Specifically, a glass plate, a polymer plate, a film, a metal plate, a film, etc. are mentioned. Examples of the glass plate include soda lime glass, barium strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like. Moreover, as a polymer board, polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, polysulfone, etc. are mentioned. As a metal plate, what contains 1 or more types of metals or alloys chosen from the group which consists of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

In the present invention, a polymer film or a metal film can be preferably used in that the organic EL device can be thinned. Furthermore, the polymer film has an oxygen permeability of 1 × 10 ⁻³ mL / (m ² · 24h · atm) or less measured by the method according to JIS K 7126-1987, and water vapor measured by the method according to JIS K 7129-1992. The transmittance (25 ± 0.5 ° C., relative humidity (90 ± 2%)) is preferably 1 × 10 ⁻³ g / (m ² / 24h) or less.

In order to process a sealing member to concave shape, sandblasting process, chemical etching process, etc. are used.

Specific examples of the adhesive include adhesives such as photocuring and thermosetting adhesives having a reactive vinyl group of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing types such as 2-cyanoacrylic acid esters. Moreover, heat and chemical hardening type (2 liquid mixture), such as an epoxy type, are mentioned. Moreover, hot melt polyamide, polyester, polyolefin is mentioned. Moreover, the ultraviolet curable epoxy resin adhesive of a cation hardening type is mentioned.

Moreover, since an organic EL element may deteriorate by heat processing, it is preferable that it can be adhesively hardened from room temperature to 80 degreeC. Moreover, you may disperse | distribute a desiccant in the said adhesive agent. Application | coating of the adhesive agent to a sealing part may use a commercially available dispenser, and may print like screen printing.

In addition, the electrode and the organic layer may be coated on the outer side of the electrode on the side opposite to the supporting substrate by sandwiching the organic layer, and the inorganic and organic layers may be formed in contact with the supporting substrate to form a sealing film. In this case, the material for forming the film may be a material having a function of inhibiting intrusion, although it causes deterioration of elements such as water and oxygen, and for example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used.

Moreover, in order to improve the fragility of the said film | membrane, it is preferable to have a laminated structure of these inorganic layers and the layer containing an organic material. There is no restriction | limiting in particular about the formation method of these films, For example, a vacuum vapor deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric plasma polymerization method, plasma CVD method, Laser CVD method, thermal CVD method, coating method and the like can be used.

It is preferable to inject an inert gas such as nitrogen or argon, an inert liquid such as hydrogen fluoride hydrocarbon or silicon oil into the gap between the sealing member and the display region of the organic EL element. Moreover, it is also possible to set it as a vacuum. Moreover, a hygroscopic compound can also be enclosed inside.

As the hygroscopic compound, for example, metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.), sulfates (eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate) Metal halides (e.g., calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchlorates (e.g., barium perchlorate, magnesium perchlorate, etc.) And the like, and anhydrous salts are suitably used in sulfates, metal halides and perchloric acids.

Shields, Shields

A protective film or a protective plate may be provided on the outer side of the sealing film or the sealing film on the side opposite to the support substrate to sandwich the organic layer in order to increase the mechanical strength of the device. In particular, when sealing is performed by the sealing film, since the mechanical strength is not necessarily high, it is preferable to provide such a protective film and a protective plate.

As a material which can be used for this, the same glass plate, the polymer plate, the film, the metal plate, the film, etc. which were used for the said sealing can be used, but it is preferable to use a polymer film from a light weight and thinning point.

<< light extraction improvement technology >>

The organic electroluminescent element emits light inside the layer having a refractive index higher than that of air (within the range of about 1.6 to 2.1 of the refractive index), and can generally extract only about 15% to 20% of the light generated in the light emitting layer. Known. This means that the light incident on the interface (the interface between the transparent substrate and the air) at an angle θ of the critical angle or more cannot be taken out to the outside of the device due to total reflection, or the light is totally reflected between the transparent electrode or the light emitting layer and the transparent substrate. This is because the light guides the transparent electrode or the light emitting layer, and consequently the light escapes in the side direction of the device.

As a method of improving the extraction efficiency of this light, for example, a method of forming irregularities on the surface of the transparent substrate and preventing total reflection at the interface between the transparent substrate and the air (for example, US Pat. Method to improve efficiency by making it photosensitive (for example, Japanese Patent Application Laid-Open No. 63-314795), or a method for forming a reflecting surface on the side of an element (for example, Japanese Patent Application Laid-Open No. Hei 1-220394) A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (for example, Japanese Patent Application Laid-Open No. 62-172691), and having a lower refractive index than the substrate between the substrate and the light emitter. A method of introducing a flat layer (for example, Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between an interlayer (including a substrate and an outer space) of any one of a substrate, a transparent electrode layer, and a light emitting layer. And the like (Japanese Patent Publication No. 11-283751 gazette).

In this invention, although these methods can be used in combination with the organic electroluminescent element of this invention, the method of introduce | transducing the flat layer which has a lower refractive index than a board | substrate between a board | substrate and a light emitting body, or the interlayer of any of a board | substrate, a transparent electrode layer, or a light emitting layer. The method of forming a diffraction grating between (included, a board | substrate and an outer space) can be used suitably.

By combining these means, the present invention can obtain a device having high brightness or more excellent durability.

If a low refractive index medium is formed between the transparent electrode and the transparent substrate to a thickness longer than the wavelength of light, the lower the refractive index of the medium is, the higher the extraction efficiency to the outside becomes.

As a low refractive index layer, an aerogel, porous silica, magnesium fluoride, a fluoropolymer etc. are mentioned, for example. Since the refractive index of a transparent substrate is generally in the range of about 1.5-1.7, it is preferable that a low refractive index layer has a refractive index of about 1.5 or less. Moreover, it is more preferable that it is 1.35 or less.

Further, the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is weakened when the thickness of the low refractive index medium becomes about the wavelength of the light and becomes the layer thickness at which the electromagnetic waves penetrating from the evanescent into the substrate.

The method of introducing a diffraction grating into an interface or a medium which causes total reflection has a feature of improving the light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction, that is, first-order diffraction or second-order diffraction. The diffraction grating is introduced by introducing a diffraction grating into any interlayer or medium (in a transparent substrate or in a transparent electrode) by total reflection or the like, and tries to extract the light out.

The diffraction grating to be introduced preferably has a two-dimensional periodic refractive index. This is because light emitted from the light emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution in only one direction, only light traveling in a specific direction is diffracted, and the light extraction efficiency is very high. I do not lose.

However, by making the refractive index distribution a two-dimensional distribution, light propagating in all directions is diffracted and the light extraction efficiency is increased.

As a position which introduce | transduces a diffraction grating, although it may be in any interlayer or medium (in a transparent substrate or a transparent electrode), the vicinity of the organic light emitting layer which is a place where light generate | occur | produces is preferable. At this time, the period of the diffraction grating is preferably within a range of about 1/2 to 3 times the wavelength of light in the medium. It is preferable that the arrangement of the diffraction grating is repeated two-dimensionally, such as a square lattice phase, a triangular lattice phase, and a honeycomb lattice phase.

<< condensing sheet >>

The organic EL device of the present invention is processed to provide a structure in the form of a microlens array, for example, on the light extraction side of the supporting substrate (substrate), or in combination with a so-called condensing sheet, thereby emitting a specific direction, for example, device light emission. By condensing in the front direction with respect to a surface, the brightness | luminance on a specific direction can be raised.

As an example of the microlens array, square pyramids having one side of 30 mu m and a vertex angle of 90 degrees are arranged in two dimensions on the light extraction side of the substrate. One side is preferably in the range of 10 to 100 µm. If smaller than this, the effect of diffraction occurs and is colored, and if too large, the thickness becomes thick, which is not preferable.

As the light collecting sheet, it is possible to use, for example, one practically used in an LED backlight of a liquid crystal display device. As such a sheet | seat, the brightness | luminance rising film (BEF) made from Sumitomo 3M company, etc. can be used, for example. As the shape of the prism sheet, for example, a substrate having a vertex angle of 90 degrees and a Δ-shaped stripe having a pitch of 50 µm may be formed on the substrate, or may be a shape in which the vertex angle is rounded, a shape in which the pitch is randomly changed, or another shape.

Moreover, in order to control the light emission angle from organic electroluminescent element, you may use a light diffusion plate and a film together with a light collecting sheet. For example, a diffusion film (light up) made by Kimoto Co., Ltd. can be used.

"Usage"

The organic EL element of this invention can be used as a display device, a display, and various light emission sources.

As a light emitting light source, for example, a lighting device (home lighting, in-car lighting), a clock or a backlight for a liquid crystal, a signboard advertisement, a signal device, a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor Although it is not limited to these, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, or a light source for illumination.

In the organic electroluminescent element of this invention, you may pattern by metal mask, an inkjet printing method, etc. at the time of film forming as needed. When patterning, only an electrode may be patterned, an electrode and a light emitting layer may be patterned, the whole element layer may be patterned, and a conventionally well-known method can be used in manufacture of an element.

<< display device >>

The organic EL element of this invention can be used for a display apparatus.

One aspect of the display apparatus of this invention provided with the organic electroluminescent element of this invention is demonstrated. Although the display device may be monochromatic or multicolored, the multicolor display device will be described here.

In the case of a multi-color display device, a shadow mask may be provided only when the light emitting layer is formed, and a film may be formed on one surface by a deposition method, a cast method, a spin coating method, an inkjet method, a printing method, or the like.

When only the light emitting layer is patterned, the method is not limited, but the vapor deposition method, the inkjet method, the spin coating method and the printing method are preferable.

The structure of the organic electroluminescent element with which a display apparatus is equipped is selected from the structural examples of the said organic electroluminescent element as needed.

In addition, the manufacturing method of an organic electroluminescent element is as showing in one form of manufacture of the organic electroluminescent element of the said this invention.

When a direct current voltage is applied to the multicolor display device thus obtained, light emission can be observed when a voltage of about 2 to 40 V is applied with a positive polarity of + and a negative polarity of-. In addition, even when a voltage is applied with the opposite polarity, no current flows and light emission hardly occurs. In addition, in the case of applying an alternating voltage, the light is emitted only when the positive electrode becomes negative and the negative electrode becomes negative. In addition, the waveform of the alternating current to apply may be arbitrary.

The multicolor display device can be used as a display device, a display, and various light emitting sources. In a display device and a display, full color display becomes possible by using three types of organic electroluminescent elements of blue, red, and green light emission.

Examples of the display device and the display include a television, a personal computer, a mobile device, an AV device, a text broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images or moving pictures, and the driving method in the case of using it as a display device for reproducing moving pictures may be either a simple matrix (passive matrix) system or an active matrix system.

Examples of the light emitting light source include home lighting, in-car lighting, backlights for clocks and liquid crystals, signage advertisements, signal signals, light sources for optical storage media, light sources for electrophotographic copiers, light sources for optical communication processors, light sources for optical sensors, and the like. The invention is not limited to these.

Hereinafter, an example of the display apparatus which has the organic electroluminescent element of this invention is demonstrated based on drawing.

1 is a schematic diagram illustrating an example of a display device configured of an organic EL element. It is a schematic diagram of a display, such as a mobile telephone, which displays image information by light emission of organic electroluminescent element.

The display 1 includes a display portion A having a plurality of pixels, a control portion B that performs image scanning of the display portion A based on image information, and a wiring for electrically connecting the display portion A and the control portion B. Part (C) or the like.

The control unit B is electrically connected through the display unit A and the wiring unit C, and sends a scan signal and an image data signal to each of the plurality of pixels based on image information from the outside, and for each scan line by the scan signal. The pixels of S1 sequentially emit light in accordance with the image data signal to perform image scanning, and display image information on the display portion A. FIG.

FIG. 2: is a schematic diagram of the display part A in FIG.

The display portion A has a wiring portion including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3, and the like on a substrate. The main members of the display portion A will be described below.

In FIG. 2, the light emitted (emission light) of the pixel 3 is taken out in the white arrow direction (lower direction).

The scanning line 5 and the plurality of data lines 6 of the wiring portion each include a conductive material, and the scanning line 5 and the data line 6 are orthogonal to the lattice shape, and are connected to the pixel 3 at positions perpendicular to each other. (The details are not shown).

When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light in accordance with the received image data.

Full-color display is attained when the color of light emission juxtaposes the pixel of a red region, the pixel of a green region, and the pixel of a blue region suitably on the same board | substrate.

Next, the light emission process of a pixel is demonstrated. 3 is a schematic diagram showing a circuit of a pixel.

The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. Full color display can be performed by juxtaposing these on the same board | substrate using the organic electroluminescent element of red, green, and blue light emission as the organic electroluminescent element 10 in several pixels.

In FIG. 3, an image data signal is applied to the drain of the switching transistor 11 from the control unit B shown in FIG. 1 via the data line 6. When a scan signal is applied from the controller B to the gate of the switching transistor 11 through the scan line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is transferred to the capacitor 13. And the gate of the driving transistor 12.

By the transfer of the image data signal, the capacitor 13 is charged in accordance with the potential of the image data signal, and the driving of the driving transistor 12 is turned on. The driving transistor 12 has a drain connected to the power supply line 7, a source connected to an electrode of the organic EL element 10, and a power supply line 7 according to the potential of the image data signal applied to the gate. The electric current is supplied to the organic EL element 10 from the.

When the scan signal is transferred to the next scan line 5 by the sequential scan of the controller B, the driving of the switching transistor 11 is turned off. However, since the capacitor 13 maintains the potential of the charged image data signal even when the driving of the switching transistor 11 is turned off, the driving of the driving transistor 12 is kept in an on state, when the next scanning signal is applied. The light emission of the organic EL element 10 is continued until now. When the next scanning signal is applied by sequential scanning, the driving transistor 12 is driven in synchronization with the scanning signal and then the organic EL element 10 emits light in accordance with the potential of the image data signal.

That is, in the light emission of the organic EL element 10, the switching transistor 11 and the driving transistor 12 which are active elements are provided to the organic EL element 10 of each of the plurality of pixels, and the plurality of pixels 3 are provided. Each organic EL element 10 emits light. Such a light emitting method is called an active matrix method.

Here, the light emission of the organic EL element 10 may be light emission of a plurality of gray levels by a multi-value image data signal having a plurality of gray level potentials, and on and off of a predetermined light emission amount by a binary image data signal. You may also. The potential of the capacitor 13 may be maintained until the next scan signal is applied, or may be discharged immediately before the next scan signal is applied.

The present invention is not limited to the above-described active matrix system, and may be a passive matrix light emission drive that emits an organic EL element in accordance with the data signal only when the scan signal is scanned.

FIG. 4 is a schematic diagram of a passive matrix system full color display device according to the display unit A of FIG. 2. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape to face each other with the pixel 3 interposed therebetween.

When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixel 3 connected to the applied scanning line 5 emits light according to the image data signal.

In the passive matrix system, there is no active element in the pixel 3, and the manufacturing cost can be reduced.

By using the organic EL element of the present invention, a display device with improved luminous efficiency is obtained.

<< lighting device >>

The organic EL element of this invention can be used for a lighting apparatus.

EMBODIMENT OF THE INVENTION One aspect of the lighting apparatus of this invention provided with the organic electroluminescent element of this invention is demonstrated.

The non-light-emitting surface of the organic EL device of the present invention was covered with a glass case, and a 300 μm-thick glass substrate was used as the sealing substrate, and an epoxy-based photocurable adhesive (Luxtrac LC0629B manufactured by Toagosei Co., Ltd.) was applied as a sealing material around. And it superimposes on this and adhere | attaches a transparent support substrate, and irradiates and hardens | cures by irradiating UV light from the glass substrate side, and the illumination apparatus as shown in FIG. 5 and FIG. 6 can be manufactured.

5 shows a schematic diagram of a lighting apparatus, and the organic EL element 101 of the present invention is covered with a glass cover 102 (also, the sealing operation by the glass cover does not allow the organic EL element 101 to come into contact with the atmosphere). And a glove box under a nitrogen atmosphere (under an atmosphere of high purity nitrogen gas having a purity of 99.999% or more).

FIG. 6 shows a sectional view of the lighting apparatus, and in FIG. 6, 105 is a cathode, 106 is an organic EL layer, and 107 is a glass substrate having a transparent electrode. In addition, the nitrogen gas 108 is filled in the glass cover 102, and the catcher 109 is provided.

Example

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "vol%" is shown. In addition, exemplary compounds 1-1 to 8-19 used in the Example correspond to specific examples 1-1 to 8-19 of the compound which has a structure represented by said General formula (1). In addition, the structures of Comparative Compounds 1 to 4 used in the Examples are shown.

Comparative Compound 1: Compounds disclosed in International Publication No. 2004/101707

Comparative Compound 2: Compounds Published in Patent No. 5644050

Comparative Compound 3: Compounds Published in Patent No. 5090413

Comparative compound 4: the compound disclosed in Unexamined-Japanese-Patent No. 2013-040159

Example 1

<< production of organic EL element 1-1 >>

On the glass substrate of 100 mm x 100 mm x 1.1 mm, patterning was performed on the board | substrate (AvanStrate Corporation make, NA-45) which formed ITO (indium tin oxide) into 100 nm-thick film as an anode. Thereafter, the transparent support substrate on which this ITO transparent electrode was installed was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

The transparent support substrate is fixed to a commercially available substrate holder of a vacuum vapor deposition apparatus, while 200 mg of HT-1 is inserted into a molybdenum resistance heating boat as a hole injection material, and HT-2 is used as a hole transporting material in another molybdenum resistance heating boat. 200 mg of the compound prepared as a dopant in a separate molybdenum resistance heating boat, 200 mg of Host-1 as a host compound in a separate molybdenum resistance heating boat, and a hole blocking material in a separate molybdenum resistance heating boat As an example, 200 mg of ET-1 was put, and 200 mg of ET-2 was put as an electron transporting material in a separate molybdenum-resistance heating boat, and it was installed in a vacuum vapor deposition apparatus.

Subsequently, the vacuum chamber was decompressed to 4 × 10 ⁻⁴ Pa, energized by heating in a heating boat containing HT-1, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second to form a hole injection layer having a layer thickness of 10 nm. Formed.

Furthermore, it energized and heated the heating boat containing HT-2, was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to form a hole transport layer having a layer thickness of 30 nm.

In addition, the heating boat containing Comparative Compound 1 and Host-1 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively, to form a light emitting layer having a layer thickness of 40 nm.

Furthermore, it energized and heated the heating boat containing ET-1, and deposited on the light emitting layer at the deposition rate of 0.1 nm / second, and formed the hole-blocking layer with a layer thickness of 10 nm.

Furthermore, it energized and heated the heating boat containing ET-2, and deposited on the hole-blocking layer at the deposition rate of 0.1 nm / second, and formed the electron carrying layer of 30 nm of layer thickness.

Subsequently, lithium fluoride was deposited on the electron transporting layer to form an electron injection layer (cathode buffer layer) having a layer thickness of 0.5 nm, and aluminum was deposited on the electron injection layer to form a cathode having a thickness of 110 nm. -1 was produced.

The compound used in a present Example has a chemical structural formula as follows.

<< Production of Organic EL Elements 1-2 to 1-10 >>

In the preparation of the organic EL device 1-1, organic EL devices 1-2 to 1-10 were produced in the same manner except that Comparative Compound 1 and Host-1 were changed to the compounds shown in Table 1.

Host-2 in Table 1 has the following chemical structural formula.

<< Evaluation of Organic EL Elements 1-1 to 1-10 >>

When evaluating the obtained organic electroluminescent element 1-1-1-10, the non-light-emitting surface of each organic electroluminescent element after preparation is covered with a glass case, and a 300 micrometer-thick glass substrate is used as a sealing substrate, and as a sealing material around Epoxy-based photocurable adhesive (Luxtrac LC0629B manufactured by Toagosei Co., Ltd.) is applied, which is stacked on the cathode to be in close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and shown in FIGS. 5 and 6. The lighting apparatus as one was produced.

The following evaluation was performed about each sample produced in this way. The evaluation results are shown in Table 1.

(1) External extraction quantum efficiency (also called luminous efficiency)

External extraction is performed using an organic EL element at room temperature (about 23 to 25 ° C.) under a constant current condition of 2.5 mA / cm ² , and measuring the emission luminance L [cd / m ² ] immediately after the start of lighting. The quantum efficiency η was calculated.

Here, the emission luminance was measured using CS-1000 (Konica Minolta Sensing Agent), and the external extraction quantum efficiency was represented by a relative value where the organic EL device 1-1 was set at 100.

(2) half life

According to the measuring method shown below, the half life was evaluated. Each organic EL element was driven with a constant current at a current giving an initial luminance of 1000 cd / m ² to obtain a time of 1/2 (500 cd / m ² ) of the initial luminance, which was taken as a measure of half-life. In addition, half life was shown by the relative value which makes organic electroluminescent element 1-1 100.

(3) drive voltage

The voltage at the time of driving the organic EL element under a constant current condition of 2.5 mA / cm ² at room temperature (about 23 ° C. to 25 ° C.) was measured, respectively. A relative value of 100 was obtained.

Drive voltage = (drive voltage of each element / drive voltage of organic EL element 1-1) × 100

In addition, the smaller the value indicates that the driving voltage is lower than that of the comparative example.

(4) voltage rise during operation

The voltage at the time of driving an organic electroluminescent element under room temperature (about 23 degreeC-25 degreeC) and the constant current conditions of 2.5 mA / cm <^2> was measured, respectively, and the voltage rise at the time of driving was calculated | required from the following calculation formula from the measurement result. In addition, the voltage rise at the time of drive was represented by the relative value which makes organic electroluminescent element 1-1 100.

Voltage increase (relative value) at the time of driving = driving voltage at the time of half luminance-initial driving voltage

The smaller value indicates that the voltage rise during driving is smaller than that of the comparative example.

(5) stability over time

Organic electroluminescent element was preserve | saved for 1 month on 60 degreeC and 70% RH conditions, and each power efficiency before and after storage was calculated | required. From each power efficiency, the power efficiency ratio was calculated | required according to the following formula, and this was made into the measure of stability over time.

Time stability (%) = (power efficiency after preservation / power efficiency before preservation) * 100

In addition, the power efficiency measured the front luminance and luminance angle dependency of each organic electroluminescent element using the spectral radiation luminance meter CS-1000 (made by Konica Minolta Sensing Co., Ltd.), and used what was calculated | required in front luminance of 1000 cd / m <^2> .

(6) second wave ratio

About the metal complex used as a dopant for each organic EL element, the emission spectrum under low temperature (about 77K) in 2-methyl THF solution was measured using the spectrophotometer F-7000 by Hitachi High-Tech Science. From the measurement results, the second wave ratio was calculated by the following formula and evaluated according to the following criteria. This confirmed that the light emission of the wavelength component longer than the maximum light emission wavelength was suppressed.

The amount of light emission at the peak wavelength which is long wave next to the second wave ratio = maximum light emission wavelength / the amount of light emission at the maximum light emission wavelength

◎: Second wave ratio is 0.4 or less

(Circle): The second wave ratio is more than 0.4 and 0.6 or less

(Triangle | delta): The 2nd wave ratio is more than 0.6 and less than 0.8

X: 2nd wave ratio is 0.8 or more

As apparent from Table 1, when the compound which has a structure represented by General formula (1) which concerns on this invention was used, it turned out that the 2nd wave ratio is predominantly small. In addition, the organic EL device using the compound having the structure represented by the general formula (1) is superior to the organic EL device of the comparative example in terms of light emission efficiency and light emission life, and is apparently low in driving voltage. It was also found that voltage rise was also suppressed and the stability over time was excellent.

Example 2

<< production of organic EL element 2-1 >>

On the glass substrate of 100 mm x 100 mm x 1.1 mm, patterning was performed on the board | substrate (AvanStrate Corporation make, NA-45) which formed ITO (indium tin oxide) into 100 nm-thick film as an anode. Thereafter, the transparent support substrate on which this ITO transparent electrode was installed was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

On this transparent support substrate, a solution in which poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate (PEDOT / PSS, manufactured by HC Stark, CLEVIO P VPAI 4083) was diluted to 70% by mass of pure water was used. After the thin film was formed by spin coating at 3000 rpm for 30 seconds, the film was dried at 200 ° C. for 1 hour to form a first hole transport layer having a layer thickness of 20 nm.

The transparent support substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, while 200 mg of HT-2 was used as a hole transporting material in a molybdenum-resistance heating boat, and a comparative compound 1 was prepared as a dopant in a separate molybdenum-resistance heating boat. 200 mg of Host-1 was put into a separate molybdenum resistance heating boat as a host compound, and 200 mg of ET-1 was put in a separate molybdenum resistance heating boat as an electron transporting material and installed in a vacuum vapor deposition apparatus.

Subsequently, the vacuum chamber was decompressed to 4 × 10 ⁻⁴ Pa, and then energized by heating in a heating boat containing HT-2, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second to form a second hole having a layer thickness of 20 nm. A transport layer was formed.

In addition, the heating boat containing Comparative Compound 1 and Host-1 was energized and heated, and co-deposited on the second hole transport layer at a deposition rate of 0.1 nm / second and 0.006 nm / second, respectively, to form a light emitting layer having a layer thickness of 40 nm.

Furthermore, it energized and heated the heating boat containing ET-1, and deposited on the light emitting layer at the deposition rate of 0.1 nm / second, and formed the electron carrying layer of 30 nm of layer thickness. In addition, the substrate temperature at the time of vapor deposition was room temperature.

Subsequently, lithium fluoride was deposited on the light emitting layer to form an electron injection layer having a layer thickness of 0.5 nm, and aluminum was deposited on the electron injection layer to form a cathode having a thickness of 110 nm to fabricate an organic EL device 2-1. .

<< Production of Organic EL Elements 2-2 to 2-8 >>

In the preparation of the organic EL device 2-1, organic EL devices 2-2 to 2-8 were produced in the same manner except that Comparative Compound 1 and Host-1 were changed to the compounds shown in Table 2.

<< Evaluation of Organic EL Elements 2-1 to 2-8 >>

When evaluating the obtained organic electroluminescent element, it sealed like the organic electroluminescent element 1-1-1-10 of Example 1, and produced and evaluated the lighting apparatus as shown in FIG. 5 and FIG.

Each sample thus produced was evaluated in the same manner as in Example 1 with respect to the external extraction quantum efficiency, half life, drive voltage, voltage rise during driving, stability over time, and the second wave ratio. The evaluation results are shown in Table 2. In addition, the measurement result of the external extraction quantum efficiency, half life, drive voltage, and the voltage rise at the time of driving in Table 2 was shown by the relative value which makes the measured value of organic electroluminescent element 2-1 100.

As apparent from Table 2, when the compound which has a structure represented by General formula (1) which concerns on this invention was used, it turned out that the 2nd wave ratio is predominantly small. In addition, the organic EL device using the compound having the structure represented by the general formula (1) is superior to the organic EL device of the comparative example in terms of light emission efficiency and light emission life, and is apparently low in driving voltage. It was also found that voltage rise was also suppressed and the stability over time was excellent.

Example 3

<< production of organic EL element 3-1 >>

On the glass substrate of 100 mm x 100 mm x 1.1 mm, patterning was performed on the board | substrate (AvanStrate Corporation make, NA-45) which formed ITO (indium tin oxide) into 100 nm-thick film as an anode. Thereafter, the transparent support substrate on which this ITO transparent electrode was installed was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

3000 rpm, using a solution obtained by diluting a poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) to 70 mass% of pure water on this transparent support substrate, After the thin film was formed by spin coating under a condition of 30 seconds, the film was dried at 200 ° C for 1 hour to form a first hole transport layer having a layer thickness of 20 nm.

The substrate was transferred to a nitrogen atmosphere, and spin-coating was performed on a first hole transport layer under a condition of 1500 rpm and 30 seconds using a solution in which 47 mg of HT-3 and 3 mg of HT-4 were dissolved in 10 mL of toluene. To form a thin film. Ultraviolet light was irradiated at 120 degreeC for 90 second, photopolymerization and crosslinking were carried out, and it vacuum-dried at 60 degreeC for 1 hour, and the 2nd hole transport layer of layer thickness about 20 nm was formed.

600 rpm, using a solution obtained by dissolving 100 mg of Host-3, 20 mg of Comparative Compound 1, 0.5 mg of D-1, and 0.2 mg of D-2 in 10 mL of butyl acetate on the second hole transport layer. Under the conditions of 30 seconds, a thin film was formed by spin coating. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and formed the light emitting layer of layer thickness about 70 nm.

Subsequently, a thin film was formed on this light emitting layer by spin coating under a condition of 1500 rpm for 30 seconds using a solution in which 50 mg of ET-3 was dissolved in 10 mL of hexafluoroisopropanol (HFIP). Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and formed the electron carrying layer of layer thickness about 20 nm.

Subsequently, the substrate was fixed to the substrate holder of the vacuum deposition apparatus, and the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa. Then, potassium fluoride was deposited on the electron transport layer to form an electron injection layer having a layer thickness of 0.4 nm. Further, aluminum was deposited on the electron injection layer to form a cathode having a thickness of 110 nm, to manufacture an organic EL device 3-1.

The compound used in a present Example has a chemical structural formula as follows.

<< Production of Organic EL Elements 3-2 to 3-8 >>

In the preparation of the organic EL device 3-1, organic EL devices 3-2 to 3-8 were produced in the same manner except that Comparative Compound 1 and Host-3 were changed to the compounds shown in Table 3.

Comparative compound 5 and Host-4 in Table 3 have the following chemical structural formulas.

Comparative compound 5: the compound disclosed in Unexamined-Japanese-Patent No. 2013-040159

<< Evaluation of Organic EL Elements 3-1 to 3-8 >>

When evaluating the obtained organic electroluminescent element, it sealed like the organic electroluminescent element 1-1-1-10 of Example 1, and produced and evaluated the lighting apparatus as shown in FIG. 5 and FIG.

Each sample thus produced was evaluated in the same manner as in Example 1 with respect to the external extraction quantum efficiency, half life, drive voltage, voltage rise during driving, stability over time, and the second wave ratio. Table 3 shows the results of the evaluation. In addition, the measurement result of the external extraction quantum efficiency, half life, drive voltage, and the voltage rise at the time of driving in Table 3 was shown by the relative value which makes the measured value of organic electroluminescent element 3-1 100.

As apparent from Table 3, when the compound which has a structure represented by General formula (1) which concerns on this invention was used, it turned out that the 2nd wave ratio is predominantly small. In addition, the organic EL device using the compound having the structure represented by the general formula (1) is superior to the organic EL device of the comparative example in terms of light emission efficiency and light emission life, and is apparently low in driving voltage. It was also found that voltage rise was also suppressed and the stability over time was excellent.

Example 4

<< production of organic EL element 4-1 >>

On the glass substrate of 100 mm x 100 mm x 1.1 mm, patterning was performed on the board | substrate (AvanStrate Corporation make, NA-45) which formed ITO (indium tin oxide) into 100 nm-thick film as an anode. Thereafter, the transparent support substrate on which this ITO transparent electrode was installed was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

On this transparent support substrate, a solution obtained by diluting a poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P Al4083) with pure water at 70 mass% was used. After the thin film was formed by spin coating, it was dried at 200 ° C. for 1 hour to form a first hole transport layer having a layer thickness of 30 nm.

On this first hole transport layer, a hole transport material Poly (N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl)) benzidine (manufactured by American Dye Source, ADS-254) Using a chlorobenzene solution, a thin film was formed by spin coating. It dried by heating at 150 degreeC for 1 hour, and formed the 2nd hole transport layer of layer thickness 40nm.

On this second hole transport layer, using a solution of butyl acetate of Host-3 as a host compound and Comparative Compound 1 as a dopant, a thin film was formed by spin coating, heated at 120 ° C. for 1 hour, and a layer thickness of 30 nm. The light emitting layer of was formed.

On this light emitting layer, the thin film was formed by the spin coating method using the 1-butanol solution of ET-4 as an electron carrying material, and the electron carrying layer of layer thickness 20nm was formed.

This board | substrate was installed in the vacuum vapor deposition apparatus, and the vacuum chamber was reduced to 4 * 10 <^-4> Pa. Subsequently, lithium fluoride was deposited on the electron transporting layer to form an electron injection layer having a layer thickness of 1.0 nm, aluminum was deposited on the electron injection layer to form a cathode having a thickness of 110 nm, and an organic EL device 4-1 was fabricated.

The compound used in a present Example has a chemical structural formula as follows.

<< Production of Organic EL Elements 4-2 to 4-10 >>

In the preparation of the organic EL device 4-1, organic EL devices 4-2 to 4-10 were produced in the same manner except that Comparative Compound 1 and Host-3 were changed to the compounds shown in Table 4.

Comparative compounds 6 and 7 in Table 4 have the following chemical structural formulas.

Comparative Compound 6: Compounds Published in Patent No. 5644050

Comparative Compound 7: A Compound Disclosed in Patent No. 5090413

<< Evaluation of Organic EL Elements 4-1 to 4-10 >>

When evaluating the obtained organic electroluminescent element, it sealed like the organic electroluminescent element 1-1-1-10 of Example 1, and produced and evaluated the lighting apparatus as shown in FIG. 5 and FIG.

Each sample thus produced was evaluated in the same manner as in Example 1 with respect to the external extraction quantum efficiency, half life, drive voltage, voltage rise during driving, stability over time, and the second wave ratio. The evaluation results are shown in Table 4. In addition, the measurement result of the external extraction quantum efficiency, half life, drive voltage, and the voltage rise at the time of driving in Table 4 was shown by the relative value which makes the measured value of organic electroluminescent element 4-1 100.

As apparent from Table 4, when the compound which has a structure represented by General formula (1) which concerns on this invention was used, it turned out that the 2nd wave ratio is predominantly small. In addition, the organic EL device using the compound having the structure represented by the general formula (1) is superior to the organic EL device of the comparative example in terms of light emission efficiency and light emission life, and is apparently low in driving voltage. It was also found that voltage rise was also suppressed and the stability over time was excellent.

Example 5

<< production of organic EL element 5-1 >>

On the glass substrate of 100 mm x 100 mm x 1.1 mm, patterning was performed on the board | substrate (AvanStrate Corporation make, NA-45) which formed ITO (indium tin oxide) into 100 nm-thick film as an anode. Thereafter, the transparent support substrate on which this ITO transparent electrode was installed was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

The transparent support substrate is fixed to a commercially available substrate holder of a vacuum vapor deposition apparatus, while 200 mg of HT-6 is used as a hole injection material in a molybdenum resistance heating boat, and HT-5 is used as a hole transporting material in another molybdenum resistance heating boat. 200 mg of the host compound as a host compound in a separate molybdenum resistance heating boat, 200 mg of Comparative Compound 1 as a dopant in a separate molybdenum resistance heating boat, D as a dopant in a separate molybdenum resistance heating boat 200 mg of -3 was put, 200 mg of D-4 was added as a dopant in the molybdenum resistance heating boat, and 200 mg of ET-5 was put as an electron transport material in the molybdenum resistance heating boat, and it installed in the vacuum vapor deposition apparatus.

Subsequently, the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, energized by heating in a heating boat containing HT-6, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second to form a hole injection layer having a layer thickness of 10 nm. Formed.

Furthermore, it energized and heated the heating boat containing HT-5, was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to form a hole transport layer having a layer thickness of 20 nm.

In addition, it was energized and heated in a heating boat containing Host-5, Comparative Compound 1, D-3, and D-4, respectively, and holed at a deposition rate of 0.1 nm / sec, 0.025 nm / sec, 0.0007 nm / sec, and 0.0002 nm / sec, respectively. Co-deposition was carried out on the transport layer to form a light emitting layer having a layer thickness of 60 nm.

Furthermore, it energized and heated the heating boat containing ET-5, and deposited on the light emitting layer at the deposition rate of 0.1 nm / second, and formed the electron carrying layer of 20 nm of layer thickness.

Subsequently, potassium fluoride was deposited on the electron transport layer to form an electron injection layer having a thickness of 0.5 nm, and aluminum was deposited on the electron injection layer to form a cathode having a thickness of 110 nm, thereby producing an organic EL device 5-1. It was.

The compound used in a present Example has a chemical structural formula as follows.

<< Production of Organic EL Elements 5-2 to 5-9 >>

In the preparation of the organic EL device 5-1, organic EL devices 5-2 to 5-9 were produced in the same manner except that Comparative Compound 1 and Host-5 were changed to the compounds shown in Table 5.

Host-6 in Table 5 has the following chemical structural formula.

<< Evaluation of Organic EL Elements 5-1 to 5-9 >>

When evaluating the obtained organic electroluminescent element, it sealed like the organic electroluminescent element 1-1-1-10 of Example 1, and produced and evaluated the lighting apparatus as shown in FIG. 5 and FIG.

Each sample thus produced was evaluated in the same manner as in Example 1 with respect to the external extraction quantum efficiency, half life, drive voltage, voltage rise during driving, stability over time, and the second wave ratio. The evaluation results are shown in Table 5. In addition, the measurement result of the external extraction quantum efficiency, half life, drive voltage, and the voltage rise at the time of driving in Table 5 was shown by the relative value which makes the measured value of organic electroluminescent element 5-1 100.

As apparent from Table 5, when the compound which has a structure represented by General formula (1) which concerns on this invention was used, it turned out that the 2nd wave ratio is predominantly small. In addition, the organic EL device using the compound having the structure represented by the general formula (1) is superior to the organic EL device of the comparative example in terms of light emission efficiency and light emission life, and is apparently low in driving voltage. It was also found that voltage rise was also suppressed and the stability over time was excellent.

Example 6

<< production of organic EL element 6-1 >>

On the glass substrate of 50 mm x 50 mm and thickness 0.7mm, ITO (indium tin oxide) was formed into a film by thickness of 120 nm as an anode, and patterning was performed. Thereafter, the transparent support substrate on which this ITO transparent electrode is provided is ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes, and then the transparent substrate is a substrate of a vacuum deposition apparatus commercially available. Fixed to the holder.

Each of the resistive heating boats in the vacuum evaporation apparatus was filled with a constituent material of each layer in an amount most suitable for device fabrication, respectively. The resistive heating boat used was made of a resistive heating material made of molybdenum or tungsten.

After reducing the vacuum degree to 1 × 10 ⁻⁴ Pa, it was energized by heating in a heating boat containing compound HT-1 and deposited on an ITO transparent electrode at a deposition rate of 0.1 nm / second to form a hole injection layer having a layer thickness of 10 nm. .

Subsequently, compound HT-2 was deposited in the same manner on the hole injection layer to form a hole transport layer having a layer thickness of 30 nm.

Subsequently, Comparative Compound 1 and Host-5 were co-deposited on the hole transport layer at a deposition rate of 0.1 nm / second so as to have 90 vol% and 10 vol%, respectively, to form a light emitting layer having a layer thickness of 30 nm.

Subsequently, ET-1 is deposited on the light emitting layer at a deposition rate of 0.1 nm / second to form a first electron transporting layer having a layer thickness of 10 nm, and thereon, ET-2 is deposited at a deposition rate of 0.1 nm / second and a layer thickness of 45 nm. A second electron transporting layer of was formed.

Further, after depositing lithium fluoride on the second electron transport layer to form an electron injection layer having a layer thickness of 1.0 nm, aluminum was deposited on the electron injection layer to form a cathode having a thickness of 100 nm.

The electrode extraction wiring was provided in the element, and covered with a can-shaped glass case filled with epoxy resin in a nitrogen glove box of 1 ppm or less in water and oxygen atmosphere, and a moisture absorbent was introduced into the package to produce an organic EL element 6-1. .

<< Production of Organic EL Elements 6-2 to 6-9 >>

In the preparation of the organic EL device 6-1, organic EL devices 6-2 to 6-9 were produced in the same manner except that Comparative Compound 1 and Host-5 were changed to the compounds shown in Table 6.

Comparative compound 8 in Table 6 has the following chemical structural formula.

Comparative Compound 8: Compound disclosed in Japanese Unexamined Patent Publication No. 2013-040159

<< Evaluation of Organic EL Elements 6-1 to 6-9 >>

When evaluating the obtained organic electroluminescent element, it sealed like the organic electroluminescent element 1-1-1-10 of Example 1, and produced and evaluated the lighting apparatus as shown in FIG. 5 and FIG.

Each sample thus produced was evaluated in the same manner as in Example 1 with respect to the external extraction quantum efficiency, half life, drive voltage, voltage rise during driving, stability over time, and the second wave ratio. The evaluation results are shown in Table 6. In addition, the measurement result of the external extraction quantum efficiency, half life, drive voltage, and the voltage rise at the time of driving in Table 6 was shown by the relative value which makes the measured value of organic electroluminescent element 6-1 100.

As apparent from Table 6, when the compound which has a structure represented by General formula (1) which concerns on this invention was used, it turned out that the 2nd wave ratio is predominantly small. In addition, the organic EL device using the compound having the structure represented by the general formula (1) is superior to the organic EL device of the comparative example in terms of light emission efficiency and light emission life, and is apparently low in driving voltage. It was also found that voltage rise was also suppressed and the stability over time was excellent.

Example 7

<< production of organic EL full-color display device >>

In the present embodiment, as shown in Figs. 7A to 7E, an organic EL full color display device was produced and evaluated. 7A to 7E show schematic configuration diagrams of the organic EL full color display device.

After the patterning was performed on the glass substrate 201 with a 100 nm film formation of the ITO transparent electrode 202 as an anode (NA45 manufactured by NH Techno Glass Co., Ltd.) at a pitch of 100 μm (see FIG. 7A), the glass substrate 201 was formed. A partition 203 (20 μm in width, 2.0 μm in thickness) of non-photosensitive polyimide was formed between the ITO transparent electrodes 202 by photolithography (see FIG. 7B).

A hole injection layer composition having the following composition was ejected and injected between the partition walls 203 on the ITO electrode 202 using an inkjet head (MJ800C manufactured by Epson), and irradiated with ultraviolet light for 200 seconds. By the drying process for a minute, the hole injection layer 204 having a layer thickness of 40 nm was formed (see Fig. 7C).

(Hole injection layer composition)

HT-3: 20 parts by mass

Cyclohexylbenzene: 50 parts by mass

Isopropyl biphenyl: 50 parts by mass

On this hole injection layer 204, the blue light emitting layer composition, the green light emitting layer composition, and the red light emitting layer composition of the following composition were respectively discharged and injected using an inkjet head, dried at 60 ° C. for 10 minutes, and the respective colors. Light emitting layers 205B, 205G, and 205R were formed (see Fig. 7D).

(Blue Emission Layer Composition)

Host-2: 0.7 parts by mass

Exemplary Compound 5-3: 0.04 parts by mass

Cyclohexylbenzene: 50 parts by mass

Isopropyl biphenyl: 50 parts by mass

(Green Emitting Layer Composition)

Host-1: 0.7 parts by mass

D-3: 0.04 parts by mass

Cyclohexylbenzene: 50 parts by mass

Isopropyl biphenyl: 50 parts by mass

(Red light emitting layer composition)

Host-1: 0.7 parts by mass

D-2: 0.04 parts by mass

Cyclohexylbenzene: 50 parts by mass

Isopropyl biphenyl: 50 parts by mass

Subsequently, an electron transport material is deposited to cover each of the light emitting layers 205B, 205G, and 205R to form an electron transport layer (not shown) having a layer thickness of 20 nm, and lithium fluoride is deposited to deposit an electron injection layer having a layer thickness of 0.6 nm (shown in FIG. ), And Al was deposited to form a cathode 206 having a thickness of 130 nm to fabricate an organic EL device (see FIG. 7E).

It was found that the produced organic EL elements exhibit blue, green, and red light emission by applying voltages to the electrodes, respectively, and can be used as full color display devices.

As mentioned above, when the compound which has a structure represented by General formula (1) which concerns on this invention is used, light emission with a low second wave ratio can be obtained predominantly. According to the present invention, it is possible to provide an organic electroluminescent element, a lighting device, and a display device having high luminous efficiency, low driving voltage, long life, small voltage rise during driving, and excellent stability over time.

Moreover, the organic electroluminescent element which has the said effect can be manufactured by a wet process.

As described above, the present invention is an organic electroluminescence having a light emission ratio of components having a longer wavelength than the maximum light emission wavelength, high light emission efficiency, low driving voltage and long light emission lifetime, small voltage rise during driving, and excellent stability over time. It is suitable for providing an element, a manufacturing method of the element, a display device and a lighting device provided with the element, and an organic electroluminescent element material used for the element.

1 display
3 pixels
5 scanning lines
6 data lines
7 power lines
10 organic EL elements
11 switching transistor
12 driving transistor
13 condenser
101 organic EL element
102 glass cover
105 cathode
106 organic EL layer
107 glass substrate with transparent electrodes
108 nitrogen gas
109 Catcher
201 glass substrate
202 ITO Transparent Electrode
203 bulkhead
204 hole injection layer
205B, 205G, 205R Light Emitting Layer
206 cathode
A display
B control unit
C wiring section

Claims (13)

An organic electroluminescent element comprising an organic layer sandwiched by at least one pair of anodes and cathodes,
An organic electroluminescent device, wherein said organic layer comprises at least one layer comprising a light emitting layer, and at least one of said organic layers contains a compound having a structure represented by the following general formula (1).

(In General Formula (1), R represents an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxyl group, and a mercapto group. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group R ₁ to R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, a heterocyclic group, or an aromatic heterocyclic group Ventilation, halogen atom, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, ureide group, acyl group, acyloxy group , Amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, nitro group, cyano group, hydroxy group, mercapto group, alkylsilyl group, arylsilyl group, alkyl phosphino group, ar Phosphino group, a phosphonic group, an aryl phosphonate group, alkylthio phosphorylation represents one selected from an aryl group and a phosphonium group-thio group.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ . m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n is 3.
However, at least 2 of adjacent R <_1> -R <_4> condenses and represents the structure of following General formula (3) or (4).)

(In General Formulas (3) and (4), Y ₂ to Y ₄ each independently represent O, S, or N-R ′, and Y ₅ or Y ₆ represents CR ″ or N. R ′ represents an alkyl group, Any group selected from a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group and an aromatic heterocyclic group, R "represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, a cyano group, And any group selected from an arylsilyl group and an arylphosphoryl group, each of Z ₅ to Z ₈ independently represents C-Rx or N, and a plurality of Rx's may be the same as or different from each other. The group equivalent to R <_1> -R < ₄ > in the said General formula (1) is represented. * Represents a coupling | bonding position with the structure represented by the said General formula (1).) delete delete The organic electroluminescent device according to claim 1, wherein in the general formula (1), R represents an alkyl group or a cyano group. The organic electroluminescent device according to claim 1, wherein in the general formula (1), Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group having a substituent at the 2-position. The organic electroluminescent device according to claim 1, wherein in the general formula (1), n represents 0. The organic electroluminescent device according to claim 1, wherein the light emitting layer contains a compound having a structure represented by the general formula (1). The organic electroluminescent device according to claim 7, wherein the light emitting layer contains at least two kinds of the compound of the general formula (1) and a compound having a HOMO level of -5.4 eV or less. It is a manufacturing method of the organic electroluminescent element which manufactures the organic electroluminescent element of Claim 1.
The manufacturing method of the organic electroluminescent element characterized by forming the layer containing the compound which has a structure represented by the said General formula (1) among the said organic layers by a wet process. The organic electroluminescent element of Claim 1 is provided, The display apparatus characterized by the above-mentioned. The organic electroluminescent element of Claim 1 is provided, The illuminating device characterized by the above-mentioned. An organic electroluminescent device material characterized by containing a compound having a structure represented by the following general formula (1).

(In General Formula (1), R represents an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfinyl group, a sulfonyl group, a nitro group, a cyano group, a hydroxyl group, and a mercapto group. Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group R ₁ to R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, a heterocyclic group, or an aromatic heterocyclic group Ventilation, halogen atom, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, ureide group, acyl group, acyloxy group , Amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, nitro group, cyano group, hydroxy group, mercapto group, alkylsilyl group, arylsilyl group, alkyl phosphino group, ar Phosphino group, a phosphonic group, an aryl phosphonate group, alkylthio phosphorylation represents one selected from an aryl group and a phosphonium group-thio group.
X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ . m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n is 3.
However, at least 2 of adjacent R <_1> -R <_4> condenses and represents the structure of following General formula (3) or (4).)

(In General Formulas (3) and (4), Y ₂ to Y ₄ each independently represent O, S, or N—R ′, and Y ₅ or Y ₆ represents CR ″ or N. R ′ represents an alkyl group, Any group selected from a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group and an aromatic heterocyclic group, R "represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an amino group, a cyano group, And any group selected from an arylsilyl group and an arylphosphoryl group, each of Z ₅ to Z ₈ independently represents C-Rx or N, and a plurality of Rx's may be the same as or different from each other. The group equivalent to R <_1> -R < ₄ > in the said General formula (1) is represented. * Represents a coupling | bonding position with the structure represented by the said General formula (1).) delete

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