KR20230117282A - Mixture and organic light emitting diode comprising the same - Google Patents

Abstract

For an organic electroluminescent device where an organic thin film layer comprising one layer or a plurality of layers containing at least a light emitting layer between a negative electrode and a positive electrode is stacked, the present invention provides a novel organic compound mixing method which selects materials in consideration of physical, thermal characteristics, etc. between two kinds of materials for a host constituting the light emitting layer and uses the mixed material as a host material to improve the light emitting efficiency and life of the organic electroluminescent device. In addition, the present invention puts the host material comprising two kinds or more of materials into an identical deposition source (or crucible) to heat and deposit the same. Accordingly, the present invention minimizes a contamination source possibly generated when the crucible is handled to prevent the intervention of impurities to an organic film and enable organic film deposition with high quality, thereby improving the efficiency and life of the electroluminescent device.

Description

Mixture and organic light emitting device comprising the same {Mixture and organic light emitting diode comprising the same}

The present invention relates to the display field, and more particularly, to an organic compound that can be used in manufacturing an organic light emitting device, which is a kind of display, and an organic light emitting device including the organic compound.

Until now, liquid crystal displays have occupied most of the flat panel displays, but efforts to develop new flat panel displays that are more economical and superior in performance and differentiated from liquid crystal displays are being actively conducted worldwide. Recently, an organic light emitting device that has been in the limelight as a next-generation flat panel display has advantages such as a low driving voltage, a fast response speed, and a wide viewing angle compared to a liquid crystal display.

The structure of the organic light emitting device is a substrate, an anode, a hole injection layer that accepts holes from the anode, a hole transport layer that transports holes, an electron blocking layer that blocks electrons from entering the hole transport layer from the light emitting layer, and a combination of holes and electrons to emit light. It consists of a light emitting layer that emits light, a hole blocking layer that blocks the entry of holes from the light emitting layer to the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, an electron injection layer that accepts electrons from the cathode, and a cathode. In some cases, the light emitting layer may be formed by doping the electron transport layer or the hole transport layer with a small amount of fluorescent or phosphorescent dye without a separate light emitting layer. can be performed simultaneously. The organic thin film layers between the two electrodes are formed by methods such as vacuum deposition, spin coating, inkjet printing, or laser thermal transfer. The reason why the organic light emitting device is manufactured in a multi-layered thin film structure is to stabilize the interface between the electrode and the organic material, and in the case of the organic material, since the difference in movement speed between holes and electrons is large, an appropriate hole transport layer and electron transport layer are used to transport holes. This is because luminous efficiency can be increased by effectively transferring electrons and holes to the light emitting layer so that the density of holes and electrons is balanced.

The driving principle of the organic light emitting device is as follows. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light emitting layer via the hole injection layer and the hole transport layer. Meanwhile, electrons are injected into the light emitting layer from the cathode via the electron injection layer and the electron transport layer, and carriers recombine in the light emitting layer region to generate excitons. This exciton changes from an excited state to a ground state, and as a result, fluorescent molecules in the light emitting layer emit light, thereby forming an image. At this time, light emission while falling to the ground state through a singlet excited state is called "fluorescence", and light emission while falling to the ground state through a triplet excited state is called "phosphorescence". In the case of fluorescence, the probability of a singlet excited state is 25% (triplet state 75%), and there is a limit in luminous efficiency, whereas when phosphorescence is used, up to 75% of the triplet state and 25% of the singlet excited state can be used for light emission. Theoretically, up to 100% internal quantum efficiency is possible.

Lifespan and efficiency are the most problematic issues in organic electroluminescent devices, and as displays become larger, these efficiency and lifespan problems must be solved. Efficiency, lifespan, driving voltage, etc. are related to each other. As the efficiency increases, the driving voltage relatively decreases. indicates a tendency to increase life expectancy. However, efficiency cannot be maximized by simply improving the organic layer. This is because long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interfacial properties, etc.) of the material is achieved.

In addition, in order to solve the light emission problem in the hole transport layer in recent organic electroluminescent devices, an auxiliary light emitting layer must be present between the hole transport layer and the light emitting layer, and different light emission auxiliary layers according to each light emitting layer (R, G, B) It is time to develop the layer. However, since the material used in the hole transport layer must have a low HOMO value, most of them have a low T1 value. As a result, excitons generated in the light emitting layer are transferred to the hole transport layer, resulting in charge unbalance in the light emitting layer. resulting in light emission at the interface of the hole transport layer.

When light is emitted from the interface of the hole transport layer, the color purity and efficiency of the organic electric element are lowered and the lifetime is shortened. Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T1 value and a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer.

On the other hand, it delays the penetration and diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of life shortening of organic electric devices, and has stable characteristics against Joule heating generated during device operation, that is, high glass transition. It is necessary to develop a hole injection layer material having a temperature. In addition, it has been reported that the low glass transition temperature of the material for the hole transport layer greatly affects the lifetime of the device according to the property that the uniformity of the surface of the thin film collapses during device operation. In addition, in the formation of OLED devices, deposition methods are mainstream, and materials that can withstand such deposition methods for a long time, that is, materials with strong heat resistance characteristics, are required.

In order to fully exhibit the excellent characteristics of the above-mentioned organic electric device, materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting auxiliary layer materials, light emitting materials, electron transport materials, electron injection materials, etc. are stable and efficient. It should be supported by materials first, but the development of stable and efficient organic layer materials for organic electric devices has not yet been sufficiently accomplished, and development of materials suitable for Deep Blue, Deep Green, Deep Red, and TADF and host in the light emitting layer Combination research on /dopants is still lacking, and therefore, the development and application of new materials are still required.

Republic of Korea Patent No. 1023423990000 Republic of Korea Patent No. 1019942380000

The present invention has been made to solve the above problems of the prior art, and after reducing the pressure of two or more materials to 760 torr or less, heating and mixing them above the melting point proportional to the pressure of the mixed materials to form an organic light emitting device. It is an object to provide a method of making a host material to be used.

In addition, an object of the present invention is to provide an organic light emitting device having improved luminous efficiency and lifespan of the organic light emitting device by heating and depositing a host material composed of two or more types of materials in the same deposition source (or crucible). to be

In addition, an object of the present invention is to provide an organic light emitting device with improved driving voltage, luminous efficiency and luminous lifetime by including a host material mixed with two or more types of materials as described above.

The present invention provides a method for preparing a mixed host material to be used in an organic light emitting device by mixing various materials, and provides a method for selecting materials by considering physical characteristics and thermal characteristics of mixed materials. In addition, it is more preferable that organic compounds represented by the following Chemical Formula 1 and Chemical Formula 2 are simultaneously used as the host material.

[Formula 1]

in the above formula

Ar1 is deuterium, tritium, hydrogen, CN, straight chain or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, Naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyridine An aromatic hydrocarbon group having 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of a midinyl group and a quinolinyl group;

Deuterium, tritium, hydrogen, CN, straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl , anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyra Hetero having 5 to 70 carbon atoms, substituted or unsubstituted with one or more selected from the group consisting of zinyl, pyrimidinyl, and quinolinyl, and containing one or more elements selected from the group consisting of S, O, N, and Si an aromatic hydrocarbon group;

G1, G2 and G3 are each independently C or N;

M1 is oxygen, sulfur, selenium, ethene, straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, or cycloalkyl group of 3 to 40 carbon atoms;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups An amino group substituted with;

R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , C1 to C40 straight chain or branched chain alkyl, C1 to C40 alkoxy, C1 to C40 thioalkyl, or C3 to C40 cycloalkyl group,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups is an amino group substituted with

[Formula 2]

in the above formula

Ar2 is deuterium, tritium, halogen, CN, CF ₃ , straight chain or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, Biphenyl, naphthyl, phenyl substituted with an anthracenyl group, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, tria 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of sol, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group Or an aromatic hydrocarbon group of

Deuterium, tritium, halogen, CN, CF ₃ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl , naphthyl, anthracenyl substituted with an anthracenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridine It is unsubstituted or substituted with one or more selected from the group consisting of one, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group, and S, O, N and A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms and containing at least one element selected from the group consisting of Si;

M2 and M3 are each independently oxygen, sulfur, selenium, straight or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups An amino group substituted with;

R10, R11, R12, R13, R14, R15, R16 and R17 are each independently hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , carbon number a straight-chain or branched-chain alkyl group of 1 to 40 carbon atoms, an alkoxy group of 1 to 40 carbon atoms, a thioalkyl group of 1 to 40 carbon atoms, or a cycloalkyl group of 3 to 40 carbon atoms;

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, Substituted or unsubstituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, and from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more selected elements;

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, and Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with one or more selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, phenanthrenyl, pyrenyl, 9,9 - It is an amino group substituted with one or more selected from the group consisting of dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

In addition, the present invention reduces the pressure of two or more kinds of materials to 760 torr or less, heats them above the melting point proportional to the pressure of the mixed materials, and uses the mixed materials as a host material to form an organic light emitting device. A method of mixing materials to improve luminous efficiency and luminous lifetime is provided.

The present invention reduces the pressure of two or more materials to 760 torr or less, heats them above the melting point proportional to the pressure of the mixed material, thermally stabilizes the mixed material, and then uses the mixed host material to achieve the luminous efficiency of the organic light emitting device. and a method of mixing a novel organic compound that improves luminescence lifetime.

In addition, the present invention is characterized in that the host material composed of two or more types of materials described above is placed in the same deposition source (or crucible) and deposited by heating, and by this method, generally using two or more types of host materials By minimizing contamination sources that may occur when handling two or more deposition sources (or crucibles), impurities are prevented from intervening in the organic film, and high-quality organic film deposition is possible, thereby improving the efficiency and lifespan of the organic light emitting device. there is.

In addition, the present invention provides an organic light emitting device with improved driving voltage, luminous efficiency and luminous lifetime by including the host material as described above.

In the organic electroluminescent device in which an organic thin film layer composed of one or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode,

The host constituting the light emitting layer is composed of a mixed host in which two or more materials are mixed, and is proportional to the pressure of the mixed materials after reducing the pressure of the two or more materials satisfying one or more of the following correlations to 760 torr or less. After thermally stabilizing the mixed material by heating it to a melting point or higher, it is preferable to form a host by putting the mixed host material into a deposition source (or crucible) of a vacuum thermal evaporation (VTE) tool and evaporating it.

|(molecular weight average of n materials) - (molecular weight of nth material)| ≤ 190

|(average melting point of n materials) - (melting point of nth material)| ≤ 90

|(average glass transition temperature of n materials) - (glass transition temperature of nth material)| ≤ 50

The |(molecular weight average of n materials) - (molecular weight of nth material)| means the absolute value of the above value.

In addition, such a host material is more preferable when organic compounds represented by the following Chemical Formula 1 and Chemical Formula 2 are simultaneously used.

[Formula 1]

in the above formula

Ar1 is deuterium, tritium, hydrogen, CN, straight chain or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, Naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyridine An aromatic hydrocarbon group having 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of a midinyl group and a quinolinyl group;

Deuterium, tritium, hydrogen, CN, straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl , anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyra Hetero having 5 to 70 carbon atoms, substituted or unsubstituted with one or more selected from the group consisting of zinyl, pyrimidinyl, and quinolinyl, and containing one or more elements selected from the group consisting of S, O, N, and Si an aromatic hydrocarbon group;

G1, G2 and G3 are each independently C or N;

M1 is oxygen, sulfur, selenium, ethene, straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, or cycloalkyl group of 3 to 40 carbon atoms;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups An amino group substituted with;

R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , C1 to C40 straight chain or branched chain alkyl, C1 to C40 alkoxy, C1 to C40 thioalkyl, or C3 to C40 cycloalkyl group,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups is an amino group substituted with

[Formula 2]

in the above formula

Ar2 is deuterium, tritium, halogen, CN, CF ₃ , straight chain or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, Biphenyl, naphthyl, phenyl substituted with an anthracenyl group, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, tria 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of sol, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group Or an aromatic hydrocarbon group of

Deuterium, tritium, halogen, CN, CF ₃ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl , naphthyl, anthracenyl substituted with an anthracenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridine It is unsubstituted or substituted with one or more selected from the group consisting of one, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group, and S, O, N and A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms and containing at least one element selected from the group consisting of Si;

M2 and M3 are each independently oxygen, sulfur, selenium, straight or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;

Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups An amino group substituted with;

R10, R11, R12, R13, R14, R15, R16 and R17 are each independently hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , carbon number a straight-chain or branched-chain alkyl group of 1 to 40 carbon atoms, an alkoxy group of 1 to 40 carbon atoms, a thioalkyl group of 1 to 40 carbon atoms, or a cycloalkyl group of 3 to 40 carbon atoms;

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, Substituted or unsubstituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, and from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more selected elements;

F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, and Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with one or more selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, phenanthrenyl, pyrenyl, 9,9 - It is an amino group substituted with one or more selected from the group consisting of dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

Hereinafter, the organic electroluminescent device of the present invention will be described as an example. However, the content exemplified below does not limit the organic electroluminescent device of the present invention.

In the method of manufacturing an organic electroluminescent device according to the present invention, first, an anode is formed by coating a substrate surface with an anode material in a conventional manner. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and water resistance. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, may be used.

Next, a hole injection layer (HIL) material is vacuum thermally deposited or spin-coated on the surface of the anode in a conventional manner to form a hole injection layer. Materials for the hole injection layer include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), and 4,4',4"-tris(3-methylphenyl). Amino) phenoxybenzene (m-MTDAPB), starburst type amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris (N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA) or IDE406 available from Idemitsu is exemplified.

A hole transport layer (HTL) material is vacuum thermally deposited or spin-coated on the surface of the hole injection layer in a conventional manner to form a hole transport layer. At this time, the hole transport layer material is bis (N- (1-naphthyl-n-phenyl)) benzidine (α-NPD), N, N'-di (naphthalen-1-yl) -N, N'-biphenyl -benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD).

A light-emitting layer (EML) material is vacuum thermally deposited or spin-coated on the surface of the hole transport layer in a conventional manner to form the light-emitting layer. The light emitting layer may be made of a single material or a host/dopant.

In general, when a compound of a single material is used as a light emitting layer, a dull peak is generated at a long wavelength due to an intermolecular interaction, and color purity is lowered, and efficiency is lowered due to a light emitting attenuation effect. Therefore, a host/dopant type light emitting layer is preferable , The dopant may be a fluorescent dopant or a phosphorescent dopant and may be a red, green or blue dopant. The dopant is a material that causes light emission by being mixed in a small amount compared to the host, and in the present invention, it may be a material used at 49% or 30% more preferably 20% or less compared to the host. These dopants can be classified into fluorescent dopants and phosphorescent dopants for singlet and triplet excitons, and the fluorescent dopants are compounds capable of emitting light from singlet excitons. As the fluorescent dopant, from amine compounds, aromatic compounds, chelate complexes such as tris (8-quinolinolato) aluminum complexes, coumarin derivatives, tetraphenyl butadiene derivatives, bisstyryl arylene derivatives, oxadiazole derivatives, etc. A compound selected according to the required emission color is preferable, and a styryl amine compound, a styryl diamine compound, an arylamine compound, an aryl diamine compound, and a fluoranthene compound are more preferable, and a condensed polycyclic amine derivative is still more preferable. The phosphorescent dopant is a compound capable of emitting light from a triplet excited state, and is not particularly limited as long as it emits light from a triplet excited state, but includes at least one metal selected from Ir, Pt, Os, Au, Cu, Re, and Ru, and a ligand. It is preferable that it is an organometallic complex containing. The ligand preferably has an orthometal bond. A metal complex containing a metal atom selected from Ir, Os, and Pt is preferable from the viewpoint that the phosphorescence quantum yield is high and the external quantum efficiency of the light emitting element can be further improved, and iridium complexes, osmium complexes, platinum complexes, etc. Orthometallized complexes of metal atoms, particularly Ir, Os, and Pt, are more preferable, iridium complexes and platinum complexes are more preferable, and orthometallated iridium complexes are particularly preferable.

As the host constituting the light emitting layer, anthracene derivatives and other naphthalene, phenanthrene, rubrene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopenta Condensed polycyclic aromatic compounds and their derivatives such as dienes, fluorenes and spirofluorenes, organometallic complexes such as tris(8-quinolinolate)aluminum, triarylamine derivatives, styrylamine derivatives, stilbene derivatives and coumarin derivatives , pyran derivatives, oxazone derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamic acid ester derivatives, diketopyrrolopyrrole derivatives, acridone derivatives, quinacridone derivatives, etc. can be used. However, it is not limited to these.

Often, the light emitting layer of an OLED exhibiting excellent lifetime and efficiency uses two hosts. In the future, it may be more desirable to use two or more kinds of hosts for phosphorescent blue (blue) or TADF in particular in terms of energy level characteristics. In this case, the fabrication of the light emitting layer using the vacuum thermal evaporation (VTE) process requires evaporation of three evaporation source materials in separate VTE deposition sources (or crucibles), which requires only two evaporation sources, a single host and Very complex and costly compared to standard two-component emissive layer with dopant (single host/single dopant). Pre-mixing two or more materials and evaporating them from one VTE deposition source (or crucible) can reduce the complexity of the fabrication process. However, co-evaporation must be stable and produce a deposited film with a composition that remains constant throughout the evaporation process. Variations in the composition of the film adversely affect device performance. To obtain stable co-evaporation from a mixture of compounds under vacuum, one assumes that the materials must have the same vacuum temperature under the same conditions. However, this may not be the only parameter to consider. When two components are mixed together, they may interact with each other and the evaporation properties of the mixture may differ from each other. On the other hand, substances with slightly different evaporation temperatures can form stable co-evaporation mixtures. Therefore, it is extremely difficult to realize stable coevaporation mixtures. For this reason, until now, when using two hosts, separate deposition sources (or crucibles) have been used for each host.

The “evaporation temperature” of a material is defined as the normal pressure of 1×10-6 Torr to 1×10-8 Torr at a deposition rate of typically 0.5 Å to 5 Å on a surface located at a set distance from the evaporation source of the material being evaporated, such as the deposition source (or crucible) of a VTE tool. Measured in a vacuum deposition tool. The various measurements described in this patent, such as temperature, pressure, deposition rate, etc., are expected to have nominal variables due to the tolerances expected in measurements that produce quantitative values understood by those skilled in the art. In addition to temperature, numerous factors, such as the miscibility of different materials and the phase transition temperature of different materials, can contribute to the ability to realize stable co-evaporation.

When the present inventors configure a host by mixing two or more materials, the two or more materials are melted at the average evaporation (deposition) temperature of the mixed materials in a sublimation purifier of 1x10-5 Torr to 1x10-8 Torr to thermally stabilize the mixed materials. It was found that stable simultaneous evaporation can be realized if the vapor is evaporated by putting it in the evaporation source (or crucible) of the VTE tool after evaporation. It has been found that two or more materials are capable of stable co-evaporation if they have similar evaporation temperatures and similar mass loss rates or similar vapor pressures. The "mass loss rate" of a substance is defined as the percentage of mass lost over time ("percent/min" or "%/min"), after reaching a constant evaporation state, at a given constant temperature for a given material in a given experiment. It is determined by measuring the time at which the first 5 to 10% of the mass of a sample of material is lost as measured by thermal gravimetric analysis (TGA) under conditions. The given constant temperature is one temperature point chosen such that the value of the mass loss rate is between about 0.05 and 0.50%/min. One skilled in the art will know that in order to compare two parameters, the experimental conditions must be consistent.

In addition, when the present inventors configure a host by mixing and evaporating two or more materials, when the following correlations are obtained for molecular weight, melting point, and glass transition temperature between two or more materials, it is deposited in a VTE tool. It has been found that stable co-evaporation can be realized when evaporated in a sauce (or crucible).

|(molecular weight average of n materials) - (molecular weight of nth material)| ≤ 190

|(average melting point of n materials) - (melting point of nth material)| ≤ 90

|(average glass transition temperature of n materials) - (glass transition temperature of nth material)| ≤ 50

The |(molecular weight average of n materials) - (molecular weight of nth material)| means the absolute value of the above value.

In the case of blue, green, and red organic light emitting devices, it is more preferable to simultaneously use the organic compound of Chemical Formula 1 and the organic compound of Chemical Formula 2 of the present invention as a host.

In particular, for a host to be used for phosphorescent blue (blue) and TADF, a method of selecting and mixing materials by heating in consideration of the physical properties and thermal properties of the materials to be mixed may be more preferable.

Optionally, an electron blocking layer (EBL) may be further formed between the hole transport layer and the light emitting layer.

An electron transport layer (ETL) material is vacuum thermally deposited or spin-coated on the surface of the light emitting layer in a conventional manner to form an electron transport layer. At this time, the electron transport layer material used is not particularly limited, and preferably tris(8-hydroxyquinolinolato) aluminum (Alq ₃ ) may be used.

Optionally, by additionally forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant together with the light emitting layer, diffusion of triplet excitons or holes into the electron transport layer can be prevented.

Formation of the hole blocking layer may be carried out by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner. In the case of the hole blocking layer material, it is not particularly limited, but preferably (8-hydroxyquinolinola To) lithium (Liq), bis(8-hydroxy-2-methylquinolinato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), LiF, and the like can be used.

An electron injection layer (EIL) material is vacuum thermally deposited or spin-coated on the surface of the electron transport layer in a conventional manner to form an electron injection layer. In this case, materials such as LiF, Liq, Li ₂ O, BaO, NaCl, and CsF may be used as the material for the electron injection layer.

A negative electrode is formed by vacuum thermal evaporation of a negative electrode material on the surface of the electron injection layer in a conventional manner.

At this time, the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like may be used. In addition, in the case of a top emission organic electroluminescent device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).

A capping layer (CPL) may be formed on the surface of the negative electrode by the composition for forming a capping layer according to the present invention.

The organic electroluminescent device according to the present invention may be manufactured in the order described above, that is, in the order of anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode, or vice versa, cathode/electron injection layer/ It may be prepared in the order of electron transport layer/light emitting layer/hole transport layer/hole injection layer/anode.

Hereinafter, the present invention will be described in more detail through examples and experimental examples of organic light emitting devices. Since these Examples and Experimental Examples are only for exemplifying the present invention, the scope of the present invention is not limited to these Examples and Experimental Examples.

<Manufacture of organic light emitting device>

Example 1

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). As a light emitting layer (EML) on the hole transport layer, co-host GH121 was put into one deposition source (or crucible) and evaporated to be used as a host, and tris(2-phenylpyridine)iridium(III) [Ir(ppy)3] as a dopant A light emitting layer having a thickness of 40 nm was formed by vacuum deposition by doping with 10 wt %. The co-host G121 mixed 30 g of Compound 1-127 of Chemical Formula 1 and 70 g of Compound 2-93 of Chemical Formula 2 at 320° C. in a sublimation purifier at a pressure of 1x10-8 Torr, and then pulverized and used the crystallized mixture. Anthracene derivative (ET-254) and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) with a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Thereafter, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl) Amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was deposited to a thickness of 65 nm. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

Example 2

Co-host GH136 is used as a host of the light emitting layer (EML), and the co-host GH136 mixes 30 g of compound 1-114 of formula 1 and 70 g of compound 2-125 of formula 2 by heating at 320 ° C. in a sublimation purifier of 1x10-8 Torr After that, an organic light emitting device was prepared in the same manner as in Example 1, except that the crystallized material was pulverized and used as a co-host.

Comparative Example 1

As a host of the light emitting layer (EML), Compound 1-127 of Chemical Formula 1 and Compound 2-93 of Chemical Formula 2 were put into separate deposition sources (or crucibles) and evaporated at a weight ratio of 3:7, except that they were used as hosts. An organic electroluminescent device was manufactured in the same manner as in Example 1.

Comparative Example 2

As a host of the light emitting layer (EML), Compound 1-114 of Formula 1 and Compound 2-125 of Formula 2 were put in separate deposition sources (or crucibles) and evaporated at a weight ratio of 3:7, except that they were used as hosts. An organic electroluminescent device was manufactured in the same manner as in Example 1.

The compounds used in the above Examples and Comparative Examples are shown below.

<Test Example: Characteristic Evaluation of Organic Electroluminescent Device>

host Voltage
(V) Efficiency
(Cd/A) T ₉₅ (hr) Example 1 GH121 3.8 102 575 Example 2 GH136 3.7 107 659 Comparative Example 1 1st host
1-127 2nd host
2-93 3.9 95 416 Comparative Example 2 1st host
1-114 2nd host
2-125 3.9 98 473

As a result of the above experiment, the organic light emitting devices of Examples 1 and 2 using the co-hosts GH121 and GH136 of the present invention as hosts compared with the conventional organic light emitting devices of Comparative Examples 1 and 2, efficiency and voltage characteristics showed markedly improved results. In particular, the organic light emitting device of Example 2 exhibited remarkably improved characteristics in voltage characteristics and luminous efficiency.

In addition, as a result of measuring the afterimage lifespan (T ₉₅ ), the organic electroluminescent devices of Comparative Example 1 and Comparative Example 2 had a lifespan of 500 hours or less, whereas Examples 1 and 2 had a long lifespan of 500 hours or more. It was confirmed to have, in particular, the organic electroluminescent device of Example 2 was confirmed to have a long lifespan of 600 hours or more. The above results are obtained by using a method for selecting materials in consideration of physical properties, thermal properties, etc. It can be seen as a result obtained because the mixed material was thermally stabilized by heating it above the melting point because the properties and thermal properties were similar. In addition, the method of selecting and mixing the materials to be mixed will produce the same results for the host to be used for blue and red organic light emitting devices, phosphorescent blue (blue), and TADF.

In addition, in the present invention, excellent results were obtained in the examples compared to the comparative examples because two types of host materials were used and one deposition source (or crucible) was used. By minimizing contamination sources that may occur when handling the deposition source (or crucible), it is possible to deposit high-quality organic films by preventing impurities from intervening in the organic films, thereby improving the efficiency and lifespan of the organic light emitting device.

Claims (9)

In the organic electroluminescent device in which an organic thin film layer composed of one or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode,
The host constituting the light emitting layer is composed of two or more types of materials, and after reducing the two or more types of materials to 760 torr or less, heating them above the melting point of the mixed materials, mixing them, putting them in one deposition source and evaporating them to form a host. An organic electroluminescent device characterized in that it is used. The organic light emitting device according to claim 1, wherein the molecular weight of n (n is 2 or more) materials constituting the host satisfies the following correlation.
|(molecular weight average of n materials) - (molecular weight of nth material)| ≤ 190 The organic light emitting device according to claim 2, wherein the melting points of n (n is 2 or more) materials constituting the host satisfy one of the following correlations.
|(average melting point of n materials) - (melting point of nth material)| ≤ 90
|(average glass transition temperature of n materials) - (glass transition temperature of nth material)| ≤ 50 [Claim 3] The organic electroluminescent device according to claim 2, wherein the host simultaneously includes an organic compound represented by Chemical Formula 1 and Chemical Formula 2 below.
[Formula 1]

in the above formula
Ar1 is deuterium, tritium, hydrogen, CN, straight chain or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, Naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyridine An aromatic hydrocarbon group having 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of a midinyl group and a quinolinyl group;
Deuterium, tritium, hydrogen, CN, straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl , anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyra Hetero having 5 to 70 carbon atoms, substituted or unsubstituted with one or more selected from the group consisting of zinyl, pyrimidinyl, and quinolinyl, and containing one or more elements selected from the group consisting of S, O, N, and Si an aromatic hydrocarbon group;
G1, G2 and G3 are each independently C or N;
M1 is oxygen, sulfur, selenium, ethene, straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, or cycloalkyl group of 3 to 40 carbon atoms;
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups An amino group substituted with;
R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , C1 to C40 straight chain or branched chain alkyl, C1 to C40 alkoxy, C1 to C40 thioalkyl, or C3 to C40 cycloalkyl group,
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups is an amino group substituted with
[Formula 2]


in the above formula
Ar2 is deuterium, tritium, halogen, CN, CF ₃ , straight chain or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, Biphenyl, naphthyl, phenyl substituted with an anthracenyl group, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, tria 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of sol, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group Or an aromatic hydrocarbon group of
Deuterium, tritium, halogen, CN, CF ₃ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl , naphthyl, anthracenyl substituted with an anthracenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridine It is unsubstituted or substituted with one or more selected from the group consisting of one, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group, and S, O, N and A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms and containing at least one element selected from the group consisting of Si;
M2 and M3 are each independently oxygen, sulfur, selenium, straight or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms,
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and unsubstituted or substituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;
Deuterium, tritium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, 1 carbon atom Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted or unsubstituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups An amino group substituted with;
R10, R11, R12, R13, R14, R15, R16 and R17 are each independently hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , carbon number a straight-chain or branched-chain alkyl group of 1 to 40 carbon atoms, an alkoxy group of 1 to 40 carbon atoms, a thioalkyl group of 1 to 40 carbon atoms, or a cycloalkyl group of 3 to 40 carbon atoms;
F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,
F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, 3 to 40 cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, Substituted or unsubstituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, and from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more selected elements;
F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, and Phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with one or more selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, phenanthrenyl, pyrenyl, 9,9 - It is an amino group substituted with one or more selected from the group consisting of dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups. The organic light emitting device according to claim 1, wherein the host is used as a blue host, green host, or red host. The organic light emitting device according to claim 2, wherein the host is used as a blue host, green host, or red host. The organic light emitting device according to claim 3, wherein the host is used as a blue host, green host, or red host. The organic light emitting device according to claim 1, wherein the ratio of deuterium to hydrogen in the chemical structure of the compound constituting the host is 5% or more compared to hydrogen. The organic electroluminescent device according to claim 1, wherein the compound constituting the host comprises tritium in its chemical structure,