KR102353985B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present application provides a compound represented by Formula 1 and an organic light emitting device including the same.

Description

Compound and organic light emitting device including the same

This application claims the benefit of the filing date of Korean Patent Application No. 10-2019-0002610, filed with the Korean Intellectual Property Office on January 9, 2019, the entire contents of which are incorporated herein by reference.

The present application relates to a compound and an organic light emitting device including the same.

An organic light emitting device is a light emitting device using an organic semiconductor material, and requires an exchange of holes and/or electrons between an electrode and an organic semiconductor material. The organic light emitting diode can be roughly divided into two types as follows according to the principle of operation. First, excitons are formed in the organic material layer by photons flowing into the device from an external light source, the excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes and used as a current source (voltage source) It is a type of light emitting device that becomes The second is a light emitting device of a type that applies a voltage or current to two or more electrodes to inject holes and/or electrons into an organic semiconductor material layer forming an interface with the electrodes, and operates by the injected electrons and holes.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron suppression layer, an electron transport layer, an electron injection layer, etc. can get In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, and high contrast.

A material used as an organic layer in an organic light emitting device may be classified into a light emitting material and a charge transporting material, such as a hole injecting material, a hole transporting material, an electron suppressing material, an electron transporting material, an electron injecting material, and the like, according to functions. The light-emitting material includes blue, green, and red light-emitting materials depending on the light-emitting color, and yellow and orange light-emitting materials necessary for realizing better natural colors.

In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and superior luminous efficiency than the host constituting the emission layer is mixed in a small amount in the emission layer, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

In order to sufficiently exhibit the excellent characteristics of the above-described organic light emitting device, materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron suppressing material, an electron transport material, an electron injection material, etc. are stable and efficient materials. The development of new materials continues to be demanded as it is supported by

Korean Patent Laid-Open Publication No. 10-2011-011579

The present application provides a compound and an organic light emitting device including the same.

An exemplary embodiment of the present application provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

A is a substituted or unsubstituted triazine group; a substituted or unsubstituted quinazoline group; Or a substituted or unsubstituted quinoxaline group,

X is a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkylsilyl group; a substituted or unsubstituted arylsilyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

m, p and q are each independently an integer of 0 to 4,

n is an integer from 0 to 5;

Another exemplary embodiment of the present application includes a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer among the organic material layers provides an organic light emitting device including the compound described above.

The compound represented by Formula 1 according to an exemplary embodiment of the present application may be used as a material for an organic material layer of an organic light emitting device.

When an organic light emitting device is manufactured using the compound represented by Formula 1 according to an exemplary embodiment of the present application, an organic light emitting device having high efficiency, low voltage and/or long lifespan may be obtained.

According to an exemplary embodiment of the present application, when benzene is introduced adjacent to the carbazoles in a Thermally Activated Delayed Fluorescence (TADF) material containing carbazoles, benzene acts as a linker in the middle of the donor/acceptor. Some of the highest peak molecular orbitals (HOMO) and lowest co-molecular orbitals (LUMO) in a molecule are mixed to increase stability and increase quantum efficiency. In addition, it is possible to control the triplet energy level by controlling the cyclic group of benzene, thereby preventing a decrease in quantum efficiency due to triplet quenching, and additionally adjusting the binding force between carbazoles and benzene to increase the lifespan. have.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9, an electron injection and transport layer ( 10) and an example of an organic light emitting device including a cathode 4 are shown.

Hereinafter, the present application will be described in more detail.

The present application relates to a novel organic compound that can be advantageously used in an organic light emitting device. In particular, the present application relates to thermally activated delayed fluorescence (TADF) materials and their use in organic light emitting devices.

A fluorescence emitting material using a phenomenon (thermal activated delayed fluorescence or thermally activated delayed fluorescence, TADF) using reverse intersystem crossing (RISC) from triplet excitons to singlet excitons, and organic Possibility of use as a light emitting device has been reported. If delayed fluorescence by the TADF material is used, even in fluorescence emission by electric field excitation, an internal quantum efficiency of 100%, which is theoretically equivalent to phosphorescence emission, becomes possible.

In order to express the TADF phenomenon, at room temperature or the temperature of the light emitting layer in the organic light emitting device, it is necessary that 75% of triplet excitons generated by electric field excitation are reversed intermittently to singlet excitons. In addition, 100% internal quantum efficiency is theoretically possible because singlet excitons generated by inverse intersystem crossover emit fluorescence similarly to 25% singlet excitons generated by direct excitation. In order for the inverse intersystem crossing to occur, the absolute value ΔEST of the difference between the lowest singlet excitation energy level S1 and the lowest triplet excitation energy level T1 is required to be small.

For example, in order to express the TADF phenomenon, it is effective to reduce ΔEST of organic compounds. It is effective to reconcile (clearly separate).

However, in the case of localization without mixing the highest occluded molecular orbital (HOMO) and lowest covalent molecular orbital (LUMO) in a molecule, the π-conjugated system in the molecule is reduced or cut, making it difficult to achieve stability and compatibility with organic light emission as a result. This will shorten the life of the device.

Accordingly, there is a demand for a new method for increasing the efficiency and lifespan of a TADF device in the art.

An exemplary embodiment of the present application provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

A is a substituted or unsubstituted triazine group; a substituted or unsubstituted quinazoline group; Or a substituted or unsubstituted quinoxaline group,

X is a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkylsilyl group; a substituted or unsubstituted arylsilyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

m, p and q are each independently an integer of 0 to 4,

n is an integer from 0 to 5;

In the compound represented by Formula 1, benzene is introduced adjacent to the carbazoles in a Thermally Activated Delayed Fluorescence (TADF) material containing carbazoles. Accordingly, since benzene acts as a linker in the middle of the donor/acceptor, some of the highest peak molecular orbital (HOMO) and lowest co-molecular orbital (LUMO) in the molecule are mixed to increase stability, It shows the effect of increasing the quantum efficiency. In addition, it is possible to control the triplet energy level by adjusting the substituent of benzene (X in Formula 1), thereby preventing a decrease in quantum efficiency due to triplet quenching, and additionally adjusting the binding force between carbazoles and benzene This can increase the lifespan.

In the present application, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In the present application, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Examples of substituents in the present application are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" includes deuterium (-D); halogen group; nitrile group; nitro group; hydroxyl group; silyl group; boron group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

Examples of the substituents are described below, but are not limited thereto.

In the present application, examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).

In the present application, the silyl group may be represented by the formula of _{-SiY a} Y _b Y _{c , wherein Y a} , Y _b and Y _c are each hydrogen; a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like, but is not limited thereto. does not

In the present application, the alkylsilyl group is a silyl group substituted with an alkyl group, and may be selected from examples of the silyl group.

In the present application, the arylsilyl group is a silyl group substituted with an aryl group, and may be selected from examples of the silyl group.

In the present application, the boron group may be represented by the formula of _{-BY d} Y _{e , wherein Y d} and Y _e are each hydrogen; a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. Specifically, the boron group includes, but is not limited to, a trimethylboron group, a triethylboron group, a tert-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

In the present application, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 30. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, etc., but are not limited thereto.

In the present application, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, and the like, but is not limited thereto. .

The substituents including alkyl groups, alkoxy groups, and other alkyl group moieties described in the present application include both straight-chain or pulverized forms.

In the present application, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but is not limited thereto.

In the present application, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 39. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, a terphenyl group, or a quaterphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto no.

In the present application, the fluorene group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오렌기,

(9,9-디메틸플루오렌기), 및

(9,9-디페닐플루오렌기) 등의 치환된 플루오렌기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorene group is substituted,

,

spirofluorene groups such as

(9,9-dimethyl fluorene group), and

It may be a substituted fluorene group such as (9,9-diphenylfluorene group). However, the present invention is not limited thereto.

In the present application, the heterocyclic group is a cyclic group including at least one of N, O, P, S, Si and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but is preferably from 2 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 2 to 36 carbon atoms. Examples of the heterocyclic group include a pyridine group, a pyrrole group, a pyrimidine group, a quinoline group, a pyridazine group, a furan group, a thiophene group, an imidazole group, a pyrazole group, a dibenzofuran group, a dibenzothiophene group, A carbazole group, a benzocarbazole group, a benzonaphthofuran group, a benzonaphthothiophene group, an indenocarbazole group, an indolocarbazole group, etc., but are not limited thereto.

In the present application, the description of the above-described heterocyclic group may be applied, except that the heteroaryl group is aromatic.

In the present application, the amine group is -NH ₂ ; monoalkylamine group; monoarylamine group; diarylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of a monoheteroarylamine group and a diheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , diphenylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group and the like, but is not limited thereto.

In the present application, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.

In the present application, a monoarylamine group; diarylamine group; The aryl group of the N-arylheteroarylamine group is the same as the above-described aryl group.

In the present application, an N-arylheteroarylamine group; The heteroaryl group of the monoheteroarylamine group and the diheteroarylamine group is the same as the above-described heteroaryl group.

According to an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of Chemical Formulas 2 to 9 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 2 to 9,

The definitions of A, X, R1 to R4, m, n, p and q are as defined in Formula 1 above.

In an exemplary embodiment of the present application, A in Formula 1 is a triazine group unsubstituted or substituted with an aryl group; a quinazoline group unsubstituted or substituted with an aryl group; Or a quinoxaline group substituted or unsubstituted with an aryl group, wherein the aryl group may be each independently substituted or unsubstituted with deuterium or an alkyl group.

In an exemplary embodiment of the present application, A in Formula 1 is a triazine group unsubstituted or substituted with a phenyl group; a quinazoline group unsubstituted or substituted with a phenyl group; Or a quinoxaline group substituted or unsubstituted with a phenyl group, wherein the phenyl group may be independently substituted or unsubstituted with deuterium or a methyl group.

In an exemplary embodiment of the present application, X in Formula 1 is a cyano group; an alkyl group; aryl group; Or a heteroaryl group substituted or unsubstituted with an aryl group, wherein the aryl group may each independently be substituted or unsubstituted with deuterium or an alkyl group.

In an exemplary embodiment of the present application, X in Formula 1 is a cyano group; methyl group; phenyl group; Or a triazine group unsubstituted or substituted with a phenyl group, wherein the phenyl group may be each independently substituted or unsubstituted with deuterium or a methyl group.

In the exemplary embodiment of the present application, R1 to R4 in Formula 1 may each independently be hydrogen or deuterium.

According to an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following compounds.

According to an exemplary embodiment of the present application, the triplet energy level of the compound represented by Formula 1 is 2.1 eV or more, preferably 2.1 eV or more and 3.0 eV or less, 2.2 eV or more and 3.0 eV or less, 2.3 eV or more It may be 2.9 eV or less. When the triplet energy level of the compound represented by Formula 1 satisfies the above range, electron injection is facilitated and the formation rate of excitons is increased, so that luminous efficiency is increased.

According to an exemplary embodiment of the present application, the difference between the singlet energy level and the triplet energy level of the compound represented by Formula 1 is 0eV or more and 0.3eV or less, and preferably 0eV or more and 0.2eV or less. . When the difference between the singlet energy level and the triplet energy level of the compound represented by Formula 1 satisfies the above range, the exciton generated from the triplet is converted to a singlet by reverse intersystem transition (RISC). As the moving rate and speed increase, the time the excitons stay in the triplet is reduced, so that the efficiency and lifespan of the organic light emitting diode are increased.

In the present application, triplet energy can be measured by using a spectrometer capable of measuring fluorescence and phosphorescence, and in the case of measurement conditions, toluene or TEF as a solvent in a cryogenic state using liquid nitrogen is used as a solution at a concentration of ^{10 -6 M} , and excluding singlet emission from the spectrum emitted by irradiating the solution with a light source in the absorption wavelength band of the material, and analyzing the spectrum emitted from triplet to confirm. When electrons are reversed from the light source, the time the electrons stay in the triplet is much longer than the time that the electrons stay in the singlet, so it is possible to separate the two components in a cryogenic state.

In the present application, singlet energy is measured using a fluorescent device, and unlike the triplet energy measurement method described above, a light source is irradiated at room temperature.

In an exemplary embodiment of the present application, compounds having various energy band gaps may be synthesized by introducing various substituents into the core structure of the compound represented by Formula 1 above. In addition, in an exemplary embodiment of the present application, the HOMO and LUMO energy levels of the compound may be controlled by introducing various substituents into the core structure of the above structure.

In addition, an organic light emitting device according to an exemplary embodiment of the present application includes a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer includes the compound represented by Formula 1 above.

The organic light emitting device according to an exemplary embodiment of the present application may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except for forming one or more organic material layers using the compound represented by Chemical Formula 1 described above. have.

When manufacturing an organic light emitting device having an organic material layer including the compound represented by Compound 1, the organic material layer may be formed by a solution coating method as well as a vacuum deposition method. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic light emitting device according to the exemplary embodiment of the present application may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device according to an exemplary embodiment of the present application includes a hole transport layer, a hole injection layer, an electron blocking layer, a layer for transporting and injecting holes at the same time as an organic material layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron It may have a structure including one or more of the layers simultaneously transporting and injecting electrons. However, the structure of the organic light emitting device according to the exemplary embodiment of the present application is not limited thereto and may include a smaller number or a larger number of organic material layers.

In the organic light emitting device according to the exemplary embodiment of the present application, the organic material layer may include a hole transport layer or a hole injection layer, and the hole transport layer or the hole injection layer may include the compound represented by Chemical Formula 1 described above.

In the organic light emitting device according to the exemplary embodiment of the present application, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include the compound represented by Chemical Formula 1 described above.

In the organic light emitting device according to the exemplary embodiment of the present application, the organic material layer may include a light emitting layer, and the light emitting layer may include the compound represented by Chemical Formula 1 described above.

According to an exemplary embodiment of the present application, the organic material layer may include an emission layer, and the emission layer may include the compound in an amount of 10 to 100 parts by weight in the emission layer.

According to an exemplary embodiment of the present application, the organic material layer may include an emission layer, and the emission layer may include the compound as a host of the emission layer.

According to an exemplary embodiment of the present application, the organic material layer may include an emission layer, and the emission layer may include the compound as a dopant of the emission layer.

In an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer includes the compound as a dopant of the light emitting layer, and may further include a host. In this case, the content of the dopant may be included in an amount of 10 parts by weight to 99 parts by weight based on 100 parts by weight of the host, preferably 30 parts by weight to 50 parts by weight.

As described above, when the compound represented by Formula 1 according to an exemplary embodiment of the present application is used as a dopant in the emission layer, the lifetime and efficiency of the device are improved. More specifically, according to an exemplary embodiment of the present application, when benzene is introduced adjacent to the carbazoles in a Thermally Activated Delayed Fluorescence (TADF) material containing carbazoles, benzene is a linker in the middle of the donor/acceptor. Because it acts as a molecular orbital (HOMO) and the lowest co-molecular orbital (LUMO) in the molecule mixed to increase the stability and increase the quantum efficiency is effective. In addition, it is possible to control the triplet energy level by controlling the cyclic group of benzene, thereby preventing a decrease in quantum efficiency due to triplet quenching, and additionally adjusting the binding force between carbazoles and benzene to increase the lifespan. have.

According to an exemplary embodiment of the present application, the organic material layer may include an emission layer, and the emission layer may include the compound as an auxiliary dopant or sensitizer of the emission layer.

According to an exemplary embodiment of the present application, the organic material layer may include an emission layer, the emission layer may include the compound, and further include a host and a fluorescent dopant. At this time, the compound serves as an auxiliary dopant or sensitizer, and specifically, the compound receives holes and electrons from the host to form excitons, It serves to transfer the generated exciton to the fluorescent dopant.

In a typical organic light emitting device, the number of excitons generated from singlets and triplets is generated at a ratio of 25:75 (singlet:triplet), and fluorescence emission, phosphorescence emission, and thermally activated delayed fluorescence according to the emission pattern according to the exciton movement It can be divided into luminescence. In the case of phosphorescence, excitons in a triplet excited state move to a ground state to emit light, and in the case of fluorescence, excitons in a singlet excited state are converted to a ground state ( ground state) and means to emit light, and the thermally activated delayed fluorescence emission is a reverse intersystem transition induced from a triplet excited state to a singlet excited state, It means that the exciton moves to the ground state to cause fluorescence.

Since the compound according to the exemplary embodiment of the present application has delayed fluorescence properties, excitons in a triplet excited state are generally reverse-transitioned to a singlet excited state by transferring the energy to a dopant. It is possible to implement an organic light emitting device having high efficiency.

In the exemplary embodiment of the present application, the first electrode is an anode, and the second electrode is a cathode.

According to another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

The organic light emitting device may have, for example, a stacked structure as follows, but is not limited thereto.

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

(2) anode/hole injection layer/hole transport layer/light emitting layer/cathode

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

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

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

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

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

(8) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

(9) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode

(10) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

(11) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode

(12) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(13) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(14) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(15) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(16) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron injection and transport layer / cathode

In the above structure, "electron transport layer/electron injection layer" may be replaced with "electron injection and transport layer".

The structure of the organic light emitting diode according to the exemplary embodiment of the present application may have the structure shown in FIGS. 1 and 2 , but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1 . In such a structure, the compound may be included in the light emitting layer 3 .

2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9, an electron injection and transport layer ( 10) and the cathode 4 are sequentially stacked, the structure of the organic light emitting device is exemplified.

For example, the organic light emitting device according to the exemplary embodiment of the present application uses a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form a metal or a metal oxide having conductivity on a substrate. Alternatively, an anode is formed by depositing an alloy thereof, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer is formed thereon, and then a material that can be used as a cathode thereon It can be prepared by vapor deposition. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a layer that simultaneously injects and transports electrons, an electron blocking layer, a light emitting layer and an electron transport layer, an electron injection layer, a layer that simultaneously injects and transports electrons, etc. However, the present invention is not limited thereto and may have a single-layer structure. In addition, the organic layer is formed using a variety of polymer materials in a smaller number by a solvent process rather than a vapor deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made in layers.

The anode is an electrode for injecting holes, and as the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present application include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode is an electrode for injecting electrons, and the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer that facilitates injection of holes from the anode to the light emitting layer. As the hole injection material, holes can be well injected from the anode at a low voltage, and the highest occupied (HOMO) of the hole injection material is The molecular orbital) is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. organic materials, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto. Specifically, the hole injection material may be a hexanitrile hexaazatriphenylene-based organic material. More specifically, the hole injection material may be hexanitrile hexaazatriphenylene-hexanitrile (HAT-CN), but is not limited thereto.

The hole injection layer may have a thickness of 1 nm to 150 nm. If the thickness of the hole injection layer is 1 nm or more, there is an advantage in that the hole injection characteristics can be prevented from being deteriorated, and if it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement There are advantages to avoiding this.

The hole transport layer may serve to facilitate hole transport. As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together. Specifically, the hole transport material may be an arylamine-based organic material. More specifically, the hole transport material may be N4,N4'-di(naphthalen-1-yl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (NPB). However, the present invention is not limited thereto.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. For the electron blocking layer, a material known in the art, for example, a heteroarylamine-based compound may be used, but is not limited thereto.

The light emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

Examples of the host material for the light emitting layer include a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. More specifically, a carbazole derivative may be used as the host material of the emission layer, but is not limited thereto.

When the emission layer emits red light, the emission dopant is PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium) ), a phosphorescent material such as octaethylporphyrin platinum (PtOEP), or a _{fluorescent material such as Alq 3} (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the emission layer emits green light, the emission dopant is a _{phosphor such as Ir(ppy) 3} (fac tris(2-phenylpyridine)iridium), Alq ₃ (tris(8-hydroxyquinolino)aluminum), anthracene-based compound, or pi A fluorescent material such as a lene-based compound or a boron-based compound may be used, but is not limited thereto. When the light-emitting layer emits blue light, the light-emitting dopant includes a _{phosphorescent material such as (4,6-F2ppy) 2} Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), A fluorescent material such as a PFO-based polymer, a PPV-based polymer, an anthracene-based compound, a pyrene-based compound, or a boron-based compound may be used, but is not limited thereto.

The electron transport layer may serve to facilitate the transport of electrons. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may have a thickness of 1 nm to 50 nm. If the thickness of the electron transport layer is 1 nm or more, there is an advantage in that the electron transport characteristics can be prevented from being deteriorated, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent an increase in the driving voltage to improve the movement of electrons. There are advantages that can be

The electron injection layer may serve to facilitate electron injection. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect with respect to the light emitting layer or the light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and , a compound having excellent thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, benzimidazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium (Liq), bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, and bis(8-hydroxyquinolinato). ) Manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo [h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolina earth)(o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, it is not limited thereto.

The electron injection and transport layer is a layer that simultaneously injects and transports electrons. As the material for the electron injection and transport layer, any material applicable to the electron injection layer and the electron transport layer may be used without limitation. For example, a benzimidazole derivative and a metal complex compound may be used simultaneously, but the present invention is not limited thereto.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Examples of the hole blocking material include, but are not limited to, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, BCP, an aluminum complex, and the like. Specifically, the hole blocking material may be a phenanthroline derivative, but is not limited thereto.

The organic light emitting device according to the exemplary embodiment of the present application may be a top emission type, a back emission type, or a double side emission type depending on a material used.

Hereinafter, examples will be given to describe the present application in detail. However, the embodiments according to the present application may be modified in various other forms, and the scope of the present application is not to be construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely explain the present specification to those of ordinary skill in the art.

production example .

The compound represented by Formula 1 may be formed by introducing various types of nitrogen-containing hetero groups into fluorophenylboronic acid substituted as follows. After introducing the nitrogen-containing hetero group, finally, the expanded form of indolocarbazole was introduced to synthesize the compounds.

production example 1-1. Synthesis of compound 1-A

(3-cyano-4-fluorophenyl)boronic acid 20g (121.3mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 121.3mmol, tetrahydrofuran 200mL and water 100mL were mixed and heated to 60 °C. Potassium carbonate (363.9 mmol) and tetrakitriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 38.9 g of compound 1-A (yield 91%).

MS[M+H]+ = 353

production example 1-2. Synthesis of compound 1-B

(4-fluoro-1,3-phenylene) diboronic acid 22.3 g (121.3 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 242.6 mmol, tetrahydrofuran 300 mL and 150 mL of water were mixed and heated to 60°C. Potassium carbonate (606.5 mmol) and tetrakistriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 62.3 g of compound 1-B (yield 92%).

MS[M+H]+ = 559

production example 1-3. Synthesis of compound 1-C

20 g (121.3 mmol) of (3-cyano-4-fluorophenyl) boronic acid, 121.3 mmol of 2-chloro-4-phenylquinazoline, 200 mL of tetrahydrofuran and 100 mL of water were mixed and heated to 60°C. Potassium carbonate (363.9 mmol) and tetrakitriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 33.2 g of compound 1-C (yield 84%).

MS[M+H]+ = 326

production example 1-4. Synthesis of compound 1-D

20 g (121.3 mmol) of (3-cyano-4-fluorophenyl) boronic acid, 121.3 mmol of 2-chloro-3-phenylquinoxaline, 200 mL of tetrahydrofuran and 100 mL of water were mixed and heated to 60°C. Potassium carbonate (363.9 mmol) and tetrakitriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 32 g of compound 1-D (yield 81%).

MS[M+H]+ = 326

production example 1-5. Synthesis of compound 1-E

(3-cyano-4-fluorophenyl) boronic acid 20 g (121.3 mmol), 2-chloro-4,6-bis (phenyl-d5) -1,3,5-triazine 121.3 mmol, tetrahydrofuran 200 mL and 100 mL of water were mixed and heated to 60°C. Potassium carbonate (363.9 mmol) and tetrakitriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 39.6 g of compound 1-E (yield 90%).

MS[M+H]+ = 363

production example 1-6. Synthesis of compound 1-F

(5-chloro-2-fluorophenyl) boronic acid 21.1 g (121.3 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 121.3 mmol, tetrahydrofuran 200 mL and water 100 mL were mixed and heated to 60 °C. Potassium carbonate (363.9 mmol) and tetrakitriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 39.5 g of compound 1-F (yield 90%).

MS[M+H]+ = 362

production example 1-7. Synthesis of compound 1-G

(2-cyano-4-fluorophenyl)boronic acid 20g (121.3mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 121.3mmol, tetrahydrofuran 200mL and water 100mL were mixed and heated to 60 °C. Potassium carbonate (363.9 mmol) and tetrakitriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 35 g of compound 1-G (yield 82%).

MS[M+H]+ = 353

production example 2-1. Synthesis of compound 2-A

Compound 1-F 35.1g (97mmol), 1,4-dioxane 350mL, potassium acetate 291mmol, pinacolactodiborane 106.7mmol, palladiumacetate 2mmol and tricyclohexylphosphine 4mmol were mixed to form a reflux state. Stirred for 20 hours. After the reaction, water was added to the reaction solution returned to room temperature, and the precipitate was washed sequentially with pure water and ethanol. This solid was purified by recrystallization from chloroform/hexane (1:1) to obtain 38.2 g of compound 2-A (yield 87%).

MS[M+H]+ = 454

production example 3-1. Synthesis of compound 3-A

Compound 2-A 34.9g (77mmol), 2-chloro-3-phenylquinoxaline 77mmol, tetrahydrofuran 200mL and water 100mL were mixed and heated to 60 ℃. Potassium carbonate (231 mmol) and tetrakistriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 32.7 g of compound 3-A (yield 80%).

MS[M+H]+ = 532

production example 3-2. Synthesis of compound 3-B

Compound 2-A 34.9g (77mmol), 2-chloro-4-phenylquinazoline 77mmol, tetrahydrofuran 200mL and water 100mL were mixed and heated to 60 ℃. Potassium carbonate (231 mmol) and tetrakistriphenylphosphine palladium (2 mmol) were added, and the mixture was stirred under reflux for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 33.1 g of compound 3-B (yield 81%).

MS[M+H]+ = 532

production example 4-1. Synthesis of compound 1

Compound 1-A 10.6 g (30 mmol) and 6-phenyl-6,11-dihydrobenzofuro [2,3-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 18.3 g of Compound 1 (yield 81%).

MS[M+H]+ = 755

production example 4-2. Synthesis of compound 2

Compound 1-A 10.6 g (30 mmol) and 10-phenyl-10,15-dihydrobenzofuro [3,2-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 18.8 g of Compound 2 (yield 83%).

MS[M+H]+ = 755

production example 4-3. Synthesis of compound 3

Compound 1-A 10.6 g (30 mmol) and 5-phenyl-5,6-dihydrobenzofuro [2,3-c] indolo [2,3-a] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 16.3 g of compound 3 (yield 72%).

MS[M+H]+ = 755

production example 4-4. Synthesis of compound 4

Compound 1-A 10.6 g (30 mmol) and 6-phenyl-5,6-dihydrobenzofuro [2,3-c] indolo [2,3-a] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 15.8 g of compound 4 (yield 70%).

MS[M+H]+ = 755

production example 4-5. Synthesis of compound 5

Compound 1-B 16.7g (30mmol) and 10-phenyl-10,15-dihydrobenzofuro[3,2-a]indolo[3,2-c]carbazole (30mmol) in 100mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 22.7 g of Compound 5 (yield 79%).

MS[M+H]+ = 961

production example 4-6. Synthesis of compound 6

9.8 g (30 mmol) of compound 1-C and 10-phenyl-10,15-dihydrobenzofuro [3,2-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 15.9 g of compound 6 (yield 73%).

MS[M+H]+ = 728

production example 4-7. Synthesis of compound 7

9.8 g (30 mmol) of compound 1-D and 10-phenyl-10,15-dihydrobenzofuro [3,2-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 16.4 g of Compound 7 (yield 75%).

MS[M+H]+ = 728

production example 4-8. Synthesis of compound 8

Compound 1-E 10.9 g (30 mmol) and 10-phenyl-10,15-dihydrobenzofuro [3,2-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 18.8 g of compound 8 (yield 82%).

MS[M+H]+ = 765

production example 4-9. Synthesis of compound 9

Compound 3-A 15.9 g (30 mmol) and 10-phenyl-10,15-dihydrobenzofuro [3,2-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 19.6 g of compound 9 (yield 70%).

MS[M+H]+ = 934

production example 4-10. Synthesis of compound 10

Compound 3-B 15.9 g (30 mmol) and 10-phenyl-10,15-dihydrobenzofuro [3,2-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 20.4 g of Compound 10 (yield 73%).

MS[M+H]+ = 934

production example 4-11. Synthesis of compound 11

Compound 1-G 10.6 g (30 mmol) and 6-phenyl-6,11-dihydrobenzofuro [2,3-a] indolo [3,2-c] carbazole (30 mmol) in 100 mL of dimethylformamide After complete dissolution, sodium-tert-butoxide (60 mmol) was added, and the mixture was heated and stirred at 80° C. for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 16.1 g of Compound 11 (yield 71%).

MS[M+H]+ = 755

Various substituents were introduced through the same synthesis process as in the above reaction scheme to synthesize the materials in the embodiment.

Experimental example One. triplet Measurement of energy levels

The triplet energy level (T1) was measured in a cryogenic state using the characteristics of a long-lived triplet exciton. Specifically, the compound is dissolved in a toluene solvent ^{to prepare a sample having a concentration of 10 -5} M, the sample is put in a quartz kit, cooled to 77K, and a 300 nm light source is irradiated to the sample for phosphorescence measurement to phosphorescence while changing the wavelength The spectrum was measured. For the measurement of the spectrum, a spectrophotometer (FP-8600 spectrophotometer, JASCO) was used.

The vertical axis of the phosphorescence spectrum was the phosphorescence intensity, and the horizontal axis was the wavelength. A tangent line was drawn with respect to the rise of the short wavelength side of the phosphorescence spectrum, the wavelength value (λ _edge1 (nm)) of the intersection of the tangent line and the horizontal axis was obtained, and then the triplet energy was calculated by substituting this wavelength value into the following conversion equation 1. .

Conversion formula (F1): T1 (eV) = 1239.85/λ _edge1

The tangent to the rise on the short-wavelength side of the phosphorescence spectrum is drawn as follows. First, among the maximum values of the spectrum, the maximum on the shortest wavelength side was confirmed. At this time, the local maximum having a peak intensity of 15% or less of the maximum peak intensity of the spectrum was not included in the maximum value on the shortest wavelength side described above. The tangent line at each point on the spectrum curve from the short wavelength side of the phosphorescence spectrum to the said local maximum was considered. Among these tangents, the tangent with the largest inclination value (that is, the tangent at the inflection point) was set as the tangent to the rise on the short-wavelength side of the phosphorescence spectrum.

Experimental example 2. single port Measurement of energy levels

The singlet energy level (S1) was measured by the following method.

^{A 10 -5} M toluene solution of the compound to be measured was prepared, put in a quartz cell, and the emission spectrum (vertical axis: luminescence intensity, horizontal axis: wavelength) of a 300 nm light source of the sample was measured at room temperature (300 K). A tangent line was drawn with respect to the rise of the short wavelength side of the emission spectrum, and the wavelength value (λ _edge2 (nm)) of the intersection of the tangent line and the horizontal axis was substituted into the following conversion equation 2 to calculate the singlet energy. The emission spectrum was measured using a spectrophotometer (FP-8600 spectrophotometer) manufactured by JASCO.

Conversion formula 2: S1(eV) = 1239.85/λ _edge2

The tangent to the rise on the short wavelength side of the emission spectrum is drawn as follows. First, among the maximum values of the spectrum, the maximum on the shortest wavelength side was confirmed. The tangent line at each point on the spectrum curve from the short wavelength side of the emission spectrum to the said local maximum was considered. Among these tangents, the tangent with the largest inclination value (that is, the tangent at the inflection point) was set as the tangent to the rise on the short wavelength side of the emission spectrum. The maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum was not included in the maximum value on the shortest wavelength side described above.

The triplet energy level (T1), the singlet energy level (S1), and the difference between the singlet energy level and the triplet energy level (ΔEST) measured by the above method are shown in Table 1 below.

compound S1 (eV) T1 (eV) △EST(eV) One 2.40 2.37 0.03 2 2.41 2.37 0.04 3 2.41 2.38 0.03 4 2.42 2.37 0.05 5 2.40 2.37 0.03 6 2.41 2.38 0.03 7 2.42 2.37 0.05 8 2.41 2.37 0.04 9 2.40 2.37 0.03 10 2.40 2.38 0.02 11 2.41 2.37 0.04

From Table 1, it can be seen that all of the compounds 1 to 11 prepared in Preparation Examples have a ΔEST of 0.3 eV or less, which is suitable as a delayed fluorescent material.

Experimental example 3. Fabrication of organic light emitting devices

comparative example 1-1.

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode by vacuum deposition. First, hexaazatriphenylene-hexanitrile (HAT-CN) was thermally vacuum deposited to a thickness of 500 Å on ITO to form a hole injection layer.

The following compound NPB was vacuum-deposited on the hole injection layer to form a hole transport layer (300 Å).

An electron blocking layer was formed by vacuum-depositing the following compound EB1 to a thickness of 100 Å on the hole transport layer.

Then, on the electron blocking layer, the following compound m-CBP and 4CzIPN to a thickness of 300 Å were vacuum-deposited at a weight ratio of 70:30 to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 to a thickness of 100 Å on the light emitting layer.

On the hole blocking layer, the following compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited in a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 2,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.70 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2x10 ^{- Maintaining 7} torr to 5x10 ^{- 6} torr, an organic light emitting device was manufactured.

Experimental example 1-1 to 1-11.

An organic light emitting diode was manufactured in the same manner as in Comparative Example 1-1, except that the compound of Table 2 below was used instead of the compound 4CzIPN in Comparative Example 1-1.

comparative example 1-2 to 1-4.

An organic light emitting diode was manufactured in the same manner as in Comparative Example 1-1, except that the following compounds Z1 to Z3 were used instead of the compound 4CzIPN in Comparative Example 1-1.

Driving voltage (V) and current efficiency (cd/A), 3000 cd measured at a current density of 10 mA/cm 2 for the organic light emitting devices of Experimental Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-4 / m and at a luminance of the ^second brightness in the CIE color coordinate and 3000cd / m ² measured at the time (T95) until the reduction to 95%, are shown in Table 2 below.

division compound
(Light emitting layer) Voltage
(V) efficiency
(cd/A) CIE color coordinates
(x,y) T95
(hr) Experimental Example 1-1 One 4.1 21 (0.22, 0.65) 91 Experimental Example 1-2 2 4.1 20 (0.23, 0.64) 90 Experimental Example 1-3 3 4.0 20 (0.23, 0.64) 92 Experimental Example 1-4 4 4.1 22 (0.23, 0.65) 92 Experimental Example 1-5 5 4.1 21 (0.22, 0.64) 90 Experimental Example 1-6 6 4.2 22 (0.22, 0.65) 93 Experimental Example 1-7 7 4.1 21 (0.22, 0.64) 91 Experimental Example 1-8 8 4.1 21 (0.23, 0.65) 90 Experimental Example 1-9 9 4.2 21 (0.23, 0.64) 91 Experimental Example 1-10 10 4.1 20 (0.22, 0.64) 93 Experimental Example 1-11 11 4.1 22 (0.22, 0.65) 91 Comparative Example 1-1 4CzIPN 4.7 15 (0.21, 0.61) 51 Comparative Example 1-2 Z1 4.7 11 (0.24, 0.61) 7 Comparative Example 1-3 Z2 4.9 10 (0.23, 0.60) 5 Comparative Example 1-4 Z3 4.8 12 (0.19, 0.52) 9

In the CIE color coordinates, it was judged that the color purity was higher as the value of (x, y) was closer to (0.170, 0.797) based on BT2020.

As shown in Table 2, the devices of Experimental Examples 1-1 to 1-11 using the compound of Formula 1 had lower voltages, and improved efficiency and lifespan than the devices using the material of Compound 4CzIPN in Comparative Example 1-1. improved

In addition, it was found that the device using the compound of Formula 1 has improved characteristics in terms of voltage, efficiency, color purity, and stability (lifespan) compared to Comparative Examples 1-2 to 1-4.

Therefore, it was confirmed that the compound according to the present invention has excellent light emitting ability and high color purity, so that it can be applied to delayed fluorescent organic light emitting devices.

comparative example 2-1.

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode by vacuum deposition. First, hexaazatriphenylene-hexanitrile (HAT-CN) was thermally vacuum deposited to a thickness of 500 Å on ITO to form a hole injection layer.

The following compound NPB was vacuum-deposited on the hole injection layer to form a hole transport layer (300 Å).

An electron blocking layer was formed by vacuum-depositing the following compound EB1 to a thickness of 100 Å on the hole transport layer.

Then, the following compounds m-CBP, 4CzIPN, and GD1 to a thickness of 300 Å were vacuum-deposited on the electron blocking layer in a weight ratio of 68:30:2 to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 to a thickness of 100 Å on the light emitting layer.

On the hole blocking layer, the following compound ET1 and the compound Lithium Quinolate (LiQ) were vacuum-deposited in a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 2,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2x10 ^{- Maintaining 7} torr to 5x10 ^{- 6} torr, an organic light emitting device was manufactured.

Experimental example 2-1 to 2-11.

An organic light emitting diode was manufactured in the same manner as in Comparative Example 2-1, except that the compound of Table 3 was used instead of the compound 4CzIPN in Comparative Example 2-1.

comparative example 2-2 to 2-4.

An organic light emitting diode was manufactured in the same manner as in Comparative Example 2-1, except that the compound of Table 3 was used instead of the compound 4CzIPN in Comparative Example 2-1.

Driving voltage (V) and current efficiency (cd/A), 3000 cd measured at a current density of 10 mA/cm 2 for the organic light emitting devices of Experimental Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4 CIE color coordinates measured at a luminance of /m ² were measured, and are shown in Table 3 below.

division compound
(Light emitting layer) Voltage
(V) efficiency
(cd/A) CIE color coordinates (x,y) Experimental Example 2-1 One 4.1 21 (0.19, 0.68) Experimental Example 2-2 2 4.2 22 (0.19, 0.67) Experimental Example 2-3 3 4.1 22 (0.20, 0.68) Experimental Example 2-4 4 4.1 21 (0.19, 0.67) Experimental Example 2-5 5 4.2 21 (0.20, 0.68) Experimental Example 2-6 6 4.2 22 (0.18, 0.69) Experimental Example 2-7 7 4.1 21 (0.19, 0.68) Experimental Example 2-8 8 4.2 21 (0.20, 0.67) Experimental Example 2-9 9 4.1 22 (0.19, 0.68) Experimental Example 2-10 10 4.1 22 (0.18, 0.68) Experimental Example 2-11 11 4.2 21 (0.18, 0.69) Comparative Example 2-1 4CzIPN 4.7 16 (0.16, 0.67) Comparative Example 2-2 Z1 4.8 12 (0.19, 0.65) Comparative Example 2-3 Z2 4.8 11 (0.19, 0.64) Comparative Example 2-4 Z3 4.7 13 (0.18, 0.67)

As shown in Table 3, the device of Experimental Examples 2-1 to 2-11 using the compound of Formula 1 had a lower voltage and improved efficiency than the device using the material of Compound 4CzIPN of Comparative Example 2-1 .

In addition, it was found that, compared to Comparative Examples 2-1 to 2-4, the characteristics of the device using the compound of Formula 1 were improved in terms of voltage and efficiency.

Therefore, it was confirmed that the compound according to the present invention has excellent light emitting ability and can tune the light emission wavelength, so that it is possible to realize an organic light emitting device with high color purity.

Although preferred experimental examples of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and detailed description of the invention, and this also falls within the scope of the invention. .

1: Substrate
2: Anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: electron blocking layer
8: light emitting layer
9: hole blocking layer
10: electron injection and transport layer

Claims (10)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
A is a triazine group unsubstituted or substituted with an aryl group; a quinazoline group unsubstituted or substituted with an aryl group; Or a quinoxaline group unsubstituted or substituted with an aryl group,
X is a cyano group; an alkyl group; aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group,
The aryl group is an alkyl group; Or substituted or unsubstituted with deuterium,
R1 to R4 are each hydrogen,
m, p and q are each independently an integer of 0 to 4,
n is an integer from 0 to 5; The compound according to claim 1, wherein Formula 1 is represented by any one of Formulas 2 to 9:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 2 to 9,
The definitions of A, X, R1 to R4, m, n, p and q are as defined in Formula 1 above. delete delete The compound according to claim 1, wherein the difference between the singlet energy level and the triplet energy level of the compound represented by Formula 1 is 0.3 eV or less. The compound according to claim 1, wherein Formula 1 is represented by any one of the following compounds:

a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound according to any one of claims 1, 2, 5 and 6 . The organic light emitting diode of claim 7 , wherein the organic material layer includes a hole transport layer or a hole injection layer, and the hole transport layer or the hole injection layer includes the compound. The organic light-emitting device of claim 7 , wherein the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound. The organic light-emitting device of claim 7 , wherein the organic material layer includes an emission layer, and the emission layer includes the compound.

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