WO2020145692A1 - Compound and organic light emitting device comprising same - Google Patents

Abstract

The present application provides a compound represented by chemical formula 1 and an organic light emitting device comprising same.

Description

Compound and organic light emitting device comprising 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, all of which is incorporated herein.

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

The organic light emitting device is a light emitting device using an organic semiconductor material, and requires exchange of holes and/or electrons between the electrode and the organic semiconductor material. The organic light emitting device can be roughly divided into two types according to the operation principle. First, excitons are formed in the organic layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and the electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is a light emitting device of the form. The second is a light emitting device in which holes and/or electrons are injected into a layer of an organic semiconductor material that interfaces with an electrode by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, 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 lose. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode and electrons are injected at the cathode, and excitons are formed when the injected holes meet the electrons. When it falls to the ground again, it will shine. It is known that such an organic light emitting device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, and high contrast.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron suppressing materials, electron transport materials, and electron injection materials, depending on their function. The light emitting materials include blue, green, and red light emitting materials, and yellow and orange light emitting materials necessary for realizing a better natural color depending on the light emitting color.

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

In order to sufficiently exhibit the excellent characteristics of the above-described organic light emitting device, materials constituting an 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, are stable and efficient materials It is supported by, and the development of new materials continues to be required.

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

One embodiment of the present application provides a compound represented by Formula 1 below.

[Formula 1]

In Chemical 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 from 0 to 4,

n is an integer from 0 to 5.

Another exemplary embodiment of the present application, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, and at least one layer of the organic material layer provides an organic light emitting device including the above-described compound.

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

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

According to an exemplary embodiment of the present application, when benzene is introduced adjacent to carbazoles in a thermally activated delayed fluorescence (TADF) material containing carbazoles, benzene acts as a linker in the middle of the donor/acceptor. There is an effect of increasing stability and increasing quantum efficiency by partially mixing the highest point molecular orbital (HOMO) and the lowest molecular orbital (LUMO) in the molecule. In addition, it is possible to control the triplet energy level by controlling the benzene ring, thereby preventing quantum efficiency reduction due to triplet quenching, and additionally adjusting the bonding force between carbazoles and benzene to increase the lifespan. have.

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 comprising the cathode 4 is shown.

1: Substrate

2: anode

3: light emitting layer

4: Cathode

5: hole injection layer

6: hole transport layer

7: electron blocking layer

8: emitting layer

9: hole blocking layer

10: electron injection and transport layer

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 organic light emitting devices. In particular, the present application relates to thermally active delayed fluorescence (TADF) materials and their use in organic light emitting devices.

Fluorescent light-emitting materials using thermally activated delayed fluorescence (TADF) and phenomena using reverse intersystem crossing (RISC) from triplet excitons to singlet excitons, and organic The possibility of use as a light emitting element has been reported. When the delayed fluorescence using the TADF material is used, even in fluorescence emission by electric field excitation, theoretically, an internal quantum efficiency of 100% equivalent to phosphorescence emission is possible.

In order to express the TADF phenomenon, an inverse crossover from 75% of triplet excitons generated by electric field excitation to singlet excitons occurs at room temperature or at the temperature of the light emitting layer in the organic light emitting device. In addition, by fluorescing the singlet excitons generated by inverse crossing between 25% and singlet excitons generated by direct excitation, an internal quantum efficiency of 100% is theoretically possible. In order for the inverse crossing to occur, it is required that the absolute value (ΔEST) of the difference between the lowest excitation singlet energy level (S1) and the lowest triplet excitation energy level (T1) is small.

For example, in order to express the TADF phenomenon, it is effective to reduce ΔEST of the organic compound, and to reduce △EST, it is localized without mixing the highest point molecular orbital (HOMO) and the lowest molecular orbital (LUMO) in the molecule. It is effective to reconcile (clearly separate).

However, in the case of localization without mixing the highest point molecular orbital (HOMO) and the lowest molecular orbital (LUMO) in the molecule, the π conjugated system in the molecule is reduced or cut, making it difficult to achieve stability and consequently organic emission. This will shorten the life of the device.

Therefore, there is a need in the art for a new method of increasing the efficiency and life of the TADF device.

One embodiment of the present application provides a compound represented by Formula 1 below.

[Formula 1]

In Chemical 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 from 0 to 4,

n is an integer from 0 to 5.

In the compound represented by Chemical Formula 1, benzene is introduced adjacent to 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 point molecular orbital (HOMO) and lowest 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 controlling the substituent of benzene (X in Chemical Formula 1), thereby preventing the reduction of quantum efficiency due to triplet quenching, and additionally controlling the bonding force between carbazoles and benzene It can increase the service life.

In the present application, when it is said that a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In the present application, when a member is said to be "on" another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.

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

The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" in this specification is deuterium (-D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Silyl group; Boron group; Alkoxy groups; Alkyl groups; Cycloalkyl group; Aryl group; And one or two or more substituents selected from the group consisting of heterocyclic groups, or substituted with two or more substituents of the above-exemplified substituents, or having no substituents. For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to 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, but is not limited to, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. 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 -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. The boron group may include, but is not limited to, trimethyl boron group, triethyl boron group, tert-butyl dimethyl boron group, triphenyl boron group, phenyl boron group, and the like.

In the present application, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group are 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, and the like, but is not limited to these.

In the present application, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. 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. .

Substituents comprising alkyl, alkoxy, and other alkyl group moieties described in this application include both straight-chain or ground 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 cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but is not limited thereto.

In the present application, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 39. According to one embodiment, the carbon number of the aryl group is 6 to 30. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, etc., as a monocyclic aryl 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 combine with each other to form a spiro structure.

When the fluorene group is substituted,

,

Spirofluorene groups, such as

(9,9-dimethylfluorene group), and

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

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

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

In the present application, the amine group is -NH ₂ ; Monoalkylamine groups; 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 are methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group , Diphenylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenyl naphthylamine group; N-biphenyl naphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenyl terphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group, and the like, but is not limited thereto.

In the present application, the N-aryl heteroarylamine group means 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-aryl heteroarylamine group is the same as the exemplified aryl group described above.

In the present application, the N-aryl heteroarylamine 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, the formula 1 may be represented by any one of the following formulas 2 to 9.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Chemical Formulas 2 to 9,

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

In one 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 unsubstituted or substituted with an aryl group, wherein the aryl group may be independently substituted or unsubstituted with a deuterium or alkyl group.

In one 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 it is a quinoxaline group unsubstituted or substituted with a phenyl group, wherein the phenyl group may be independently substituted or unsubstituted with deuterium or methyl groups.

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

In one embodiment of the present application, X in Chemical 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 independently substituted or unsubstituted with deuterium or methyl groups.

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

According to an exemplary embodiment of the present application, the 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 2.1eV or more, preferably 2.1eV or more and 3.0eV or less, 2.2eV or more, 3.0eV or less, 2.3eV or more It may be 2.9 eV or less. When the triplet energy level of the compound represented by Chemical Formula 1 satisfies the above range, electron injection is facilitated and the exciton formation rate is increased, so that the 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 0 eV or more and 0.3 eV or less, and preferably 0 eV or more and 0.2 eV or less . When the difference between the singlet energy level and the triplet energy level of the compound represented by Chemical Formula 1 satisfies the above range, the exciton generated in the triplet is converted into a singlet by inverse transition (RISC). As the moving rate and speed increase, the time for the exciton to stay in the triplet decreases, so there is an advantage of increasing the efficiency and life of the organic light emitting device.

In the present application, the triplet energy can be measured using a spectral instrument capable of measuring fluorescence and phosphorescence, and in the case of measurement conditions, a solution at a concentration of 10 ^-6 M using toluene or thiophene as a solvent in a cryogenic state using liquid nitrogen It is confirmed by analyzing the spectrum emitted from the triplet, except for singlet emission from the spectrum emitting light by irradiating the light source of the absorption wavelength band of the material to the solution. When the electron is reversed from the light source, the time for the electron to stay in the triplet is much longer than the time in the singlet, so it is possible to separate the two components in the cryogenic state.

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

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

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

The organic light emitting device according to the exemplary embodiment of the present application may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that one or more organic material layers are formed 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, it may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method. Here, the solution application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

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 multilayer 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 is a hole transport layer, a hole injection layer, an electron blocking layer, a layer simultaneously performing hole transport and hole injection, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron as an organic material layer It may have a structure including at least one layer of the layer for simultaneous transport and electron injection. 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 a compound represented by 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 electron injection layer may include a compound represented by Formula 1 described above.

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

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

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

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

In one embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer includes the compound as a dopant in the light emitting layer, and may further include a host. At this time, the content of the dopant may be included in 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 Chemical Formula 1 according to an exemplary embodiment of the present application is used as a dopant in the light emitting layer, the life and efficiency of the device are improved. More specifically, according to an exemplary embodiment of the present application, when benzene is introduced adjacent to carbazoles in a thermally activated delayed fluorescence (TADF) material containing carbazoles, benzene is a linker in the middle of the donor/acceptor. Since it acts as a molecule, the highest peak molecular orbit (HOMO) and the lowest molecular orbit (LUMO) in the molecule are mixed to improve stability and increase quantum efficiency. In addition, it is possible to control the triplet energy level by controlling the benzene ring, thereby preventing the reduction of quantum efficiency due to triplet quenching, and additionally adjusting the bonding force between carbazoles and benzene to increase the lifespan. have.

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

According to an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer includes the compound, and may further include a host and a fluorescent dopant. At this time, the compound acts as an auxiliary dopant or a sensitizer. Specifically, the compound receives holes and electrons from a host to form excitons, It plays a role of delivering the generated exciton to a fluorescent dopant.

In a typical organic light emitting device, the number of excitons generated in singlet and triplet is generated at a ratio of 25:75 (single term: triplet), and fluorescent emission, phosphorescence emission, and thermal activation delayed fluorescence depending on the emission type according to exciton movement It can be divided into luminescence. In the case of the phosphorescence emission, it means that the exciton of the triplet excited state moves to the ground state and emits light, and in the case of the fluorescent emission, the exciton of the singlet excited state is the ground state ( It means that it moves to the ground state and emits light, and the thermally activated delayed fluorescence emission reverses the transition from the triplet excited state to the singlet excited state, and the singlet excited state. It means that the exciton moves to the ground state and causes fluorescence emission.

As the compound according to an exemplary embodiment of the present application has a delayed fluorescence property, excitons in a triplet excited state are generally reverse-transferred to a singlet excited state to transfer the energy as a dopant It is possible to implement an organic light emitting device having high efficiency.

In one 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 described below, 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 transporting layer/electron blocking layer/light emitting layer/electron transporting layer/cathode

(8) anode/hole transporting layer/electron blocking layer/light emitting layer/electron transporting 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 transporting layer/light emitting layer/hole blocking layer/electron transporting 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 device according to the exemplary embodiment of the present application may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.

1 illustrates the 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.

In Fig. 2, the substrate 1, the anode 2, the hole injection layer 5, the hole transport layer 6, the electron blocking layer 7, the light emitting layer 8, the hole blocking layer 9, the electron injection and transport layer ( 10) and the structure of the organic light emitting device in which the cathode 4 is sequentially stacked is illustrated.

For example, the organic light emitting device according to an exemplary embodiment of the present application uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and a metal oxide having a metal or conductivity on a substrate Alternatively, an anode is formed by depositing these alloys, 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 depositing. In addition to this method, an organic light emitting device may be made by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

The organic material layer may be a multi-layer structure including a hole injection layer, a hole transport layer, a layer that simultaneously performs electron injection and electron transport, an electron blocking layer, a light emitting layer and an electron transport layer, an electron injection layer, and a layer that simultaneously performs electron injection and electron transport. However, the present invention is not limited thereto, and may be a single-layer structure. In addition, the organic material layer has a smaller number of solvent processes, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, using a variety of polymer materials. Can be prepared in layers.

The positive electrode is an electrode for injecting holes, and a positive electrode material is preferably a material having a large work function to facilitate hole injection into an organic material layer. Specific examples of the positive electrode 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); A combination of metal and oxide such as ZnO: Al or SnO ₂ : 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 an 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; There is a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer that serves to smoothly inject holes from the anode to the light emitting layer. As the hole injection material, a hole injection material can be well injected with holes from the anode, and HOMO (highest occupied) of the hole injection material It is preferable that the molecular orbital is 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 matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based organic matter. Organic materials, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto. Specifically, the hole injection material may be 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. When the thickness of the hole injection layer is 1 nm or more, there is an advantage of preventing the hole injection characteristics from being deteriorated. 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 is an advantage that can be prevented.

The hole transport layer may serve to facilitate the transport of holes. As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable for a material having high mobility for holes. Examples of the hole transport material include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion, but are not limited thereto. 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, it is not limited thereto.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron blocking layer may be a material known in the art, for example, a heteroarylamine compound, 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. As the light-emitting material, a material capable of emitting light in the visible region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV)-based polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

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

When the light-emitting layer emits red light, PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium are used as the light emitting dopant. ), phosphorescent materials such as octaethylporphyrin platinum (PtOEP), and fluorescent materials such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used, but are not limited thereto. When the light emitting layer emits green light, a phosphorescent material such as Ir(ppy) ₃ (fac tris(2-phenylpyridine)iridium) is used as a light emitting dopant, but Alq ₃ (tris(8-hydroxyquinolino)aluminum), anthracene-based compound, pi Fluorescent materials such as ren-based compounds and boron-based compounds may be used, but are not limited thereto. When the light emitting layer emits blue light, a phosphorescent material such as (4,6-F2ppy) ₂ Irpic is used as a light emitting dopant, but spiro-DPVBi, spiro-6P, distylbenzene (DSB), distriarylene (DSA), Fluorescent materials such as PFO-based polymers, PPV-based polymers, anthracene-based compounds, pyrene-based compounds, and boron-based compounds may be used, but are 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 well from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The thickness of the electron transport layer may be 1 nm to 50 nm. When the thickness of the electron transport layer is 1 nm or more, there is an advantage of preventing the electron transport properties from deteriorating, and when it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from rising to improve the movement of electrons. There is an advantage.

The electron injection layer may serve to facilitate injection of electrons. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, , A compound having excellent thin film formation ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, benzoimidazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. Their derivatives, 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, 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 Sat) (o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, etc. There is, but is not limited to this.

The electron injection and transport layer is a layer that performs electron injection and transport simultaneously. As the electron injection and transport layer material, any material applicable to the electron injection layer and the electron transport layer can be used without limitation. For example, benzoimidazole derivatives and metal complex compounds may be used simultaneously, but are not limited thereto.

The hole blocking layer is a layer that prevents the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Examples of hole blocking materials include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, 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 an exemplary embodiment of the present application may be a front emission type, a back emission type, or a double-sided emission type, depending on the material used.

Hereinafter, examples will be described in detail to specifically describe the present application. However, the embodiments according to the present application may be modified in various other forms, and the scope of the present application is not interpreted to be limited to the embodiments described below. The embodiments of the present application are provided to more fully describe the present specification to those skilled in the art.

Manufacturing example .

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

Manufacturing example 1-1. Synthesis of Compound 1-A

(3-cyano-4-fluorophenyl) boronic acid 20 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 tetrakistriphenylphosphine palladium (2 mmol) were added and stirred for 3 hours in a reflux state. 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

Manufacturing 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 water were mixed and heated to 60°C. Potassium carbonate (606.5 mmol) and tetrakistriphenylphosphine palladium (2 mmol) were added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 62.3 g of compound 1-B (yield 92%).

MS[M+H]+ = 559

Manufacturing example 1-3. Synthesis of Compound 1-C

(3-cyano-4-fluorophenyl) boronic acid 20 g (121.3 mmol), 2-chloro-4-phenylquinazoline 121.3 mmol, tetrahydrofuran 200 mL and water 100 mL were mixed and heated to 60°C. Potassium carbonate (363.9 mmol) and tetrakistriphenylphosphine palladium (2 mmol) were added and stirred for 3 hours in a reflux state. 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

Manufacturing example 1-4. Synthesis of Compound 1-D

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

MS[M+H]+ = 326

Manufacturing 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 tetrakistriphenylphosphine palladium (2 mmol) were added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 39.6 g of compound 1-E (yield 90%).

MS[M+H]+ = 363

Manufacturing 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 tetrakistriphenylphosphine palladium (2 mmol) were added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 39.5 g of compound 1-F (yield 90%).

MS[M+H]+ = 362

Manufacturing example 1-7. Synthesis of Compound 1-G

(2-cyano-4-fluorophenyl) boronic acid 20 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 tetrakistriphenylphosphine palladium (2 mmol) were added and stirred for 3 hours in a reflux state. 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

Manufacturing example 2-1. Synthesis of Compound 2-A

Compound 1-F 35.1 g (97 mmol), 350 mL of 1,4-dioxane, 291 mmol of potassium acetate, 106.7 mmol of pinalactodiborane, 2 mmol of palladium acetate, and 4 mmol of tricyclohexylphosphine were mixed to reflux. Stir 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 with chloroform/hexane (1:1) to obtain 38.2 g of compound 2-A (yield 87%).

MS[M+H]+ = 454

Manufacturing example 3-1. Synthesis of Compound 3-A

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

MS[M+H]+ = 532

Manufacturing example 3-2. Synthesis of Compound 3-B

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

MS[M+H]+ = 532

Manufacturing example 4-1. Synthesis of Compound 1

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

MS[M+H]+ = 755

Manufacturing example 4-2. Synthesis of Compound 2

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

MS[M+H]+ = 755

Manufacturing example 4-3. Synthesis of Compound 3

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

MS[M+H]+ = 755

Manufacturing example 4-4. Synthesis of Compound 4

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

MS[M+H]+ = 755

Manufacturing 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 dimethylformamide 100mL After complete dissolution, sodium-tert-butoxide (60 mmol) was added, followed by heating and stirring at 80°C for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 22.7 g of compound 5 (yield 79%).

MS[M+H]+ = 961

Manufacturing example 4-6. Synthesis of Compound 6

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

MS[M+H]+ = 728

Manufacturing 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 (30mmol) were added to 100 mL of dimethylformamide. After complete dissolution, sodium-tert-butoxide (60 mmol) was added, followed by heating and stirring at 80°C for 6 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 16.4 g of compound 7 (yield 75%).

MS[M+H]+ = 728

Manufacturing example 4-8. Synthesis of Compound 8

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

MS[M+H]+ = 765

Manufacturing example 4-9. Synthesis of Compound 9

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

MS[M+H]+ = 934

Manufacturing example 4-10. Synthesis of Compound 10

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

MS[M+H]+ = 934

Manufacturing example 4-11. Synthesis of Compound 11

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

MS[M+H]+ = 755

Substituents were synthesized by variously introducing substituents through the same synthetic process as the above scheme.

Experimental Example One. Triplet Energy level Measure

The triplet energy level (T1) was measured at a cryogenic condition using the characteristics of a triplet exciton with a long lifetime. Specifically, after dissolving the compound 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 irradiated with a 300 nm light source for a phosphorescence measurement sample to change the phosphorescence Spectra were measured. A spectrophotometer (FP-8600 spectrophotometer, JASCO) was used to measure the spectrum.

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, and the wavelength value (λ _edge1 (nm)) of the intersection of the tangent line and the horizontal axis was determined, and the wavelength value was substituted into the following conversion formula 1 to calculate the triplet energy. .

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

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

Experimental Example 2. Singlet Measurement of energy level

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, placed in a quartz cell, and the emission spectrum (vertical axis: emission intensity, horizontal axis: wavelength) of the 300 nm light source of the sample at room temperature (300K) was measured. A tangent line was drawn with respect to the rise of the short wavelength side of this emission spectrum, and the wavelength value (λ _edge2 (nm)) at the intersection of the tangent line and the horizontal axis was substituted into Equation 2 below to calculate the singlet energy. The emission spectrum was measured using a JASCO spectrophotometer (FP-8600 spectrophotometer).

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

The tangent to the rise of the short wavelength side of the emission spectrum was drawn as follows. First, the maximum value of the shortest wavelength side among the maximum values of the spectrum was confirmed. The tangent at each point on the spectrum curve from the short wavelength side of the emission spectrum to the maximum value was considered. The tangent with the largest inclination value (that is, the tangent at the inflection point) among these tangents was used as the tangent to the rise on the short wavelength side of the emission spectrum. The maximum point having the 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

Through Table 1, it can be seen that all of Compounds 1 to 11 prepared in Preparation Example have a ΔEST of 0.3 eV or less and are suitable as a delayed fluorescent material.

Experimental Example 3. Manufacturing of organic light emitting device

Comparative example 1-1.

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

An electron blocking layer was formed by vacuum-depositing the following compound EB1 with a thickness of 100 mm 2 on the hole transport layer.

Subsequently, the compound m-CBP and 4CzIPN having a thickness of 300 mm 3 were vacuum deposited on the electron blocking layer 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 with a thickness of 100 mm 2 on the light emitting layer.

On the hole blocking layer, the following compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 300 Pa. On the electron injection and transport layer, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 2,000 순차적 were sequentially deposited to form a negative electrode.

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

Experimental Example 1-1 to 1-11.

An organic light emitting diode was manufactured according to the same method as Comparative Example 1-1 except for using the compound of Table 2 below instead of the compound 4CzIPN in Comparative Example 1-1.

Comparative example 1-2 to 1-4.

An organic light emitting diode was manufactured according to the same method as Comparative Example 1-1 except for using the compounds of Z1 to Z3 below instead of the compound 4CzIPN in Comparative Example 1-1.

The driving voltage (V) and the 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 coordinate (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

As for the CIE color coordinate, it was determined that the color purity is higher as the value of (x, y) approaches (0.170, 0.797) based on BT2020.

As shown in Table 2, the device of Experimental Examples 1-1 to 1-11 using the compound of Formula 1 has a lower voltage and a higher efficiency and lifespan than the device using the compound 4CzIPN in Comparative Example 1-1. Improved.

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

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

Comparative example 2-1.

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

An electron blocking layer was formed by vacuum-depositing the following compound EB1 with a thickness of 100 mm 2 on the hole transport layer.

Subsequently, the following compounds m-CBP, 4CzIPN and GD1 were deposited under vacuum at a weight ratio of 68:30:2 with a film thickness of 300 mm 2 over the electron blocking layer to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 with a thickness of 100 mm 2 on the light emitting layer.

On the hole blocking layer, the following compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 300 Pa. On the electron injection and transport layer, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 2,000 순차적 were sequentially deposited to form a negative electrode.

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

Experimental Example 2-1 to 2-11.

An organic light emitting diode was manufactured according to the same method as Comparative Example 2-1, except for using the compound of Table 3 instead of the compound 4CzIPN in Comparative Example 2-1.

Comparative example 2-2 to 2-4.

An organic light emitting diode was manufactured according to the same method as Comparative Example 2-1, except for using the compound of Table 3 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 The CIE color coordinates measured at the 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 coordinate (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 of the compound 4CzIPN of Comparative Example 2-1. .

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

Accordingly, it was confirmed that the compound according to the present invention has excellent luminescence ability and is capable of tuning the emission wavelength, thereby realizing an organic light emitting device having high color purity.

Although the preferred experimental example of the present invention has been described through the above, the present invention is not limited to this, and it is possible to carry out various modifications within the scope of the claims and the detailed description of the invention, and this also belongs to the scope of the invention. .

Claims (10)

1. Compound represented by the formula (1):

   [Formula 1]

   

   In Chemical 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 from 0 to 4,

   n is an integer from 0 to 5.
2. The method according to claim 1, wherein Formula 1 is a compound represented by any one of the following Formulas 2 to 9:

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   [Formula 5]

   

   [Formula 6]

   

   [Formula 7]

   

   [Formula 8]

   

   [Formula 9]

   

   In Chemical Formulas 2 to 9,

   The definitions of A, X, R1 to R4, m, n, p and q are as defined in Formula 1.
3. The method according to claim 1, 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 unsubstituted or substituted with an aryl group,

   The aryl group is a compound that is each independently substituted or unsubstituted with deuterium or alkyl groups.
4. The method according to claim 1, X in Formula 1 is a cyano group; Alkyl groups; Aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group,

   The aryl group is a compound that is each independently substituted or unsubstituted with deuterium or alkyl groups.
5. The method according to claim 1, The difference between the singlet (singlet) energy level and the triplet (triplet) energy level of the compound represented by the formula (1) is 0.3 eV or less.
6. The method according to claim 1, wherein Formula 1 is a compound represented by any one of the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   
7. A first electrode; A second electrode provided to face the first electrode; And at least one layer of an organic material provided between the first electrode and the second electrode, and at least one layer of the organic material layer comprises a compound according to any one of claims 1 to 6.
8. The organic light emitting device of claim 7, wherein the organic material layer includes a hole transport layer or a hole injection layer, and the hole transport layer or a hole injection layer contains the compound.
9. The method according to claim 7, The organic material layer comprises an electron transport layer or an electron injection layer, the electron transport layer or the electron injection layer is an organic light emitting device comprising the compound.
10. The organic light emitting device of claim 7, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound.

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