KR20220099599A - Compound, coating composition comprising same, organic light emitting device using same and method of manufacturing same - Google Patents

Abstract

The present specification relates to a compound of chemical formula 1, a coating composition comprising the same, an organic light emitting device using the same, and a method for manufacturing the same. Since the compound according to one embodiment of the present specification exhibits resistance to a specific solvent, a solution process is possible. Accordingly, it is possible to increase the area of the device.

Description

Compound, coating composition comprising same, organic light emitting device using same, and method for manufacturing the same

The present specification relates to a compound, a coating composition including the compound, an organic light emitting device formed using the coating composition, and a method for manufacturing the same.

The organic light emitting phenomenon is one example in which electric current is converted into visible light by an internal process of a specific organic molecule. The principle of the organic light emitting phenomenon is as follows. When an organic material layer is placed between the anode and the cathode, when a current is applied between the two electrodes, electrons and holes are injected into the organic material layer from the cathode and the anode, respectively. Electrons and holes injected into the organic layer recombine to form excitons, and the excitons fall back to the ground state and emit light. An organic light emitting device using this principle may be generally composed of a cathode and an anode and an organic layer disposed therebetween, for example, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

Conventionally, a deposition process has been mainly used to manufacture an organic light emitting device. However, there is a problem that a lot of material loss occurs when manufacturing an organic light emitting device through the deposition process. It is being developed, and the development of a material that can be used in the solution process is required.

A material used in an organic light emitting device for a solution process should have the following properties.

First, it must be possible to form a storable homogeneous solution. Commercially available materials for the deposition process have good crystallinity, so they do not dissolve well in a solution, or crystals are easily captured even when a solution is formed.

Second, the material used for the solution process must have excellent coating properties so that a thin film of a uniform thickness can be formed without holes or agglomeration when forming a thin film.

Third, the layers subjected to the solution process must have resistance to solvents and materials used in the process of forming other layers, and are required to have excellent current efficiency and excellent lifespan characteristics when manufacturing an organic light emitting device.

Accordingly, there is a demand for the development of new organic materials in the art.

Korean Patent Publication No. 2013-106255

The present specification provides a compound, a coating composition comprising the same, an organic light emitting device using the same, and a manufacturing method thereof.

An exemplary embodiment of the present specification provides a compound of Formula 1 below.

[Formula 1]

In Formula 1,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

Ra to Rd are the same as or different from each other, and are each independently represented by the following formula (2),

[Formula 2]

In Formula 2,

L1 is a direct bond; a substituted or unsubstituted arylene group; or -L3-N(Ar2)-;

L2 is a direct bond; Or a substituted or unsubstituted arylene group,

L3 is a substituted or unsubstituted arylene group,

Y1 is a curing group,

Ar1, Ar2, and R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n1 is an integer from 1 to 5,

m1 is an integer from 1 to 3,

m2 is an integer from 1 to 4,

When n1 is 2 or more, L1 of 2 or more are the same as or different from each other,

When m1 and m2 are each 2 or more, the substituents in parentheses are the same as or different from each other,

는 화학식 1에 결합되는 부위이다.

is a site bound to Formula 1.

Another exemplary embodiment of the present specification provides a coating composition comprising the compound.

Another embodiment of the present specification is a first electrode; a second electrode; and at least one organic material layer comprising a light emitting layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers provides an organic light emitting device comprising the above-described coating composition or a cured product thereof .

Another embodiment of the present specification comprises the steps of preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer provides a method of manufacturing an organic light emitting device comprising the step of forming one or more organic material layers using the coating composition do.

Since the compound according to an exemplary embodiment of the present specification exhibits resistance to a specific solvent, a solution process is possible. Accordingly, it is possible to increase the area of the device.

In addition, since the compound according to an exemplary embodiment of the present specification has a tetrahedral structure in terms of three-dimensional geometry, it is possible to maintain a close bond, thereby improving the stability of the device when applied to an organic light emitting device. .

Accordingly, the compound according to the exemplary embodiment of the present specification may be applied to the organic material layer of the organic light emitting device, thereby improving the performance and lifespan characteristics of the device.

1 is a view showing a connection structure of a general compound.
2 is a diagram illustrating a connection structure of a compound having a three-dimensional structure.
3 and 4 are diagrams illustrating the structure of an organic light emitting device according to an exemplary embodiment of the present specification.
5 is a diagram showing the results of NMR measurement of Compound 1.

Hereinafter, the present specification will be described in detail.

An exemplary embodiment of the present specification provides a compound of Formula 1 below.

[Formula 1]

In Formula 1,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

Ra to Rd are the same as or different from each other, and are each independently represented by the following formula (2),

[Formula 2]

In Formula 2,

L1 is a direct bond; a substituted or unsubstituted arylene group; or -L3-N(Ar2)-;

L2 is a direct bond; Or a substituted or unsubstituted arylene group,

L3 is a substituted or unsubstituted arylene group,

Y1 is a curing group,

Ar1, Ar2, and R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n1 is an integer from 1 to 5,

m1 is an integer from 1 to 3,

m2 is an integer from 1 to 4,

When n1 is 2 or more, L1 of 2 or more are the same as or different from each other,

When m1 and m2 are each 2 or more, the substituents in parentheses are the same as or different from each other,

는 화학식 1에 결합되는 부위이다.

is a site bound to Formula 1.

1 is a view showing a connection structure of a general compound. When a compound having a general structure, not a three-dimensional structure, as shown in FIG. 1 is applied to an organic light emitting device, the compound has a linear structure by bonding between the compound and the compound. In this case, the degree of freedom of coupling of the linear structure is high, and thus instability is increased, and accordingly, there is a problem in that the performance or lifespan of the device is deteriorated due to degradation.

On the other hand, as shown in FIG. 2 , the compound according to an exemplary embodiment of the present specification having a three-dimensional structure has a structure in which bonds between the compounds are tightly fixed. As a result, structural stability is increased, thereby exhibiting an effect of improving performance and/or lifespan when applied to a device.

That is, since the compound according to an exemplary embodiment of the present specification has a tetrahedral structure in terms of three-dimensional geometry as shown in FIG. 2, it is possible to maintain a close bond, so that when applied to an organic light emitting device, performance and / or improved stability.

As an example, assuming that the length of the carbon bond is generally 0.154 nm and an organic material layer having a thickness of 50 nm is formed in the device, since about 16 molecules can be stacked in the organic material layer, a dense bond as shown in FIG. 2 can be formed.

In addition, since the compound according to an exemplary embodiment of the present specification includes a curing group, it exhibits resistance to a specific solvent. Accordingly, since it is advantageous to maintain a film after film formation during device manufacturing, there is an advantage that it can be applied to a solution process.

For example, since crosslinking is formed by heat treatment or light treatment in the step of forming the organic material layer using the compound, the organic material layer including the thinned structure can be provided. In addition, when another layer is laminated on the surface of the formed organic material layer, it can be prevented from being dissolved, morphologically affected, or decomposed by a solvent.

In addition, in the case of the compound according to an exemplary embodiment of the present specification, an organic light emitting device may be manufactured by a solution coating method, and thus a large area of the device may be possible.

In the present specification, 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 exists between the two members.

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

As used herein, the term “crosslinking group” may refer to a reactive substituent that crosslinks compounds between compounds by exposure to heat and/or light. Crosslinking may be generated while radicals generated while decomposing carbon-carbon multiple bonds or cyclic structures are connected by heat treatment or light irradiation.

In the present specification, the “crosslinking group” may be replaced with “thermosetting group or photocurable group”.

Hereinafter, the substituents of the present specification will be described in detail.

및

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

and

refers to a site bonded to another substituent or a bonding group.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to 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, the position where the substituent is substitutable, When two or more substituents are substituted, the two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; an alkyl group; cycloalkyl group; alkoxy group; aryloxy group; amine 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 specification, examples of the halogen group include fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

In the present specification, 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. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like.

In this specification, although carbon number of a cycloalkyl group is not specifically limited, It is preferable that it is 3-60. According to an exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 30. Specific examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably from 1 to 30 carbon atoms. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, iso pentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, and the like, but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; an alkylamine group; an arylalkylamine group; arylamine group; an aryl heteroarylamine group; It may be selected from the group consisting of an alkylheteroarylamine group and a heteroarylamine group, but is not limited thereto. The number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 60.

In the present specification, the aryl group is not particularly limited, but may have 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 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

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

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

spirofluorenyl groups such as

(9,9-dimethyl fluorenyl group), and

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

In the present specification, the aryl group of the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, but preferably has 2 to 30 carbon atoms. In an exemplary embodiment of the present specification, the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, an acridine group. , pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group, phenanthroline group, isoxazole group, thia There are a diazole group, a phenothiazine group, a dibenzofuran group, and the like, but is not limited thereto.

In the present specification, the aryloxy group is a group represented by -OR ₁₀₀ , and R ₁₀₀ is an aryl group. The aryl group in the aryloxy group is the same as the example of the aryl group described above. Specifically, the aryloxy group includes a phenoxy group, benzyloxy, p-methylbenzyloxy, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p -tert-butylphenoxy group, 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naph tyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, etc., but only these It is not limited.

이다.In the present specification, the adamantyl group

to be.

In an exemplary embodiment of the present specification, L1 is a substituted or unsubstituted arylene group; or -L3-N(Ar2)-.

In an exemplary embodiment of the present specification, L1 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; or -L3-N(Ar2)-.

In an exemplary embodiment of the present specification, L1 is a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; Or a substituted or unsubstituted biphenylene group; or -L3-N(Ar2)-.

In an exemplary embodiment of the present specification, L1 is a substituted or unsubstituted biphenylene group; or -L3-N(Ar2)-.

In an exemplary embodiment of the present specification, L1 is a biphenylene group; or -L3-N(Ar2)-.

In an exemplary embodiment of the present specification, n1 is 1, and L1 is a biphenylene group.

In an exemplary embodiment of the present specification, n1 is 2, and two L1s are a substituted or unsubstituted arylene group and -L3-N(Ar2)-, respectively.

In an exemplary embodiment of the present specification, L3 is an arylene group.

In an exemplary embodiment of the present specification, L3 is a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; or a substituted or unsubstituted biphenylene group.

In an exemplary embodiment of the present specification, L3 is a substituted or unsubstituted phenylene group.

In an exemplary embodiment of the present specification, L3 is a phenylene group.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently represents a substituted or unsubstituted C6-C30 aryl group.

In an exemplary embodiment of the present specification, Ar2 is a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, Ar2 is a substituted or unsubstituted C6-C30 aryl group.

In an exemplary embodiment of the present specification, Ar2 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; or a substituted or unsubstituted fluorene group.

In the exemplary embodiment of the present specification, Ar2 is a substituted or unsubstituted fluorene group.

In an exemplary embodiment of the present specification, Ar2 is a fluorene group substituted with one or more selected from the group consisting of an alkyl group, an aryl group, and a curing group.

In an exemplary embodiment of the present specification, Ar2 is a substituted or unsubstituted 9,9-diphenylfluorenyl group.

In an exemplary embodiment of the present specification, Ar2 is a 9,9-diphenylfluorenyl group unsubstituted or substituted with one or more of an alkyl group and a curing group.

In the exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,

m1, m2, Ar1, L2, Y1 and R1 to R3 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In the exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-3 or 2-4.

[Formula 2-3]

[Formula 2-4]

In Formulas 2-3 and 2-4,

m1, m2, Ar1, L2, Y1 and R1 to R3 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, the curing group is any one of the following structures.

In the structure,

L10 to L13 are the same as or different from each other, and each independently a direct bond; -O-; Or a substituted or unsubstituted alkylene group,

은 화학식 2에 결합되는 부위이다.

is a site bound to Formula 2;

In one embodiment of the present specification, the curing group is any one of the following structures.

In the above structure, L10 and L12 are the same as or different from each other, and each independently a direct bond; -O-; Or a substituted or unsubstituted alkylene group,

은 화학식 2에 결합되는 부위이다.

is a site bound to Formula 2;

In one embodiment of the present specification, L10 and L12 are each a direct bond.

In the exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-5 or 2-6.

[Formula 2-5]

[Formula 2-6]

In Formulas 2-5 and 2-6,

m1, m2, Ar1 and R1 to R3 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, R3 is a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, R3 is a substituted or unsubstituted C6-C30 aryl group.

In an exemplary embodiment of the present specification, R3 is an aryl group unsubstituted or substituted with an alkyl group.

In an exemplary embodiment of the present specification, R3 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; or a substituted or unsubstituted biphenyl group.

In an exemplary embodiment of the present specification, R3 is a substituted or unsubstituted phenyl group.

In an exemplary embodiment of the present specification, R3 is a phenyl group unsubstituted or substituted with an alkyl group.

In an exemplary embodiment of the present specification, R3 is a phenyl group unsubstituted or substituted with a methyl group or a tert-butyl group.

In an exemplary embodiment of the present specification, Chemical Formula 2 is represented by the following Chemical Formula 2-7 or 2-8.

[Formula 2-7]

[Formula 2-8]

In Formulas 2-7 and 2-8,

m1, m2, Ar1, R1 and R2 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R10 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

m3 is an integer from 1 to 5,

When m3 is 2 or more, two or more R10 are the same as or different from each other.

In an exemplary embodiment of the present specification, R10 is hydrogen; or a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R10 is hydrogen; or a substituted or unsubstituted C 1 to C 10 alkyl group.

In an exemplary embodiment of the present specification, R10 is hydrogen; methyl group; ethyl group; Profile group; or a tert-butyl (t-Bu) group.

In an exemplary embodiment of the present specification, R10 is hydrogen; methyl group; or a tert-butyl group.

In an exemplary embodiment of the present specification, L5 is a substituted or unsubstituted aryl group.

In the exemplary embodiment of the present specification, L5 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L5 is an arylene group.

In an exemplary embodiment of the present specification, L5 is a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; or a substituted or unsubstituted biphenylene group.

In an exemplary embodiment of the present specification, L5 is a substituted or unsubstituted phenylene group.

In an exemplary embodiment of the present specification, L5 is a phenylene group.

In an exemplary embodiment of the present specification, L6 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L6 is an arylene group.

In an exemplary embodiment of the present specification, L6 is a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; or a substituted or unsubstituted biphenylene group.

In an exemplary embodiment of the present specification, L6 is a substituted or unsubstituted biphenylene group.

In an exemplary embodiment of the present specification, L6 is a biphenylene group.

In an exemplary embodiment of the present specification, L7 is a substituted or unsubstituted arylene group.

In an exemplary embodiment of the present specification, L7 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L7 is an arylene group.

In an exemplary embodiment of the present specification, L7 is a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; or a substituted or unsubstituted biphenylene group.

In an exemplary embodiment of the present specification, L7 is a substituted or unsubstituted biphenylene group.

In an exemplary embodiment of the present specification, L7 is a biphenylene group.

In an exemplary embodiment of the present specification, Ar1 and Ar5 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, Ar1 and Ar5 are the same as or different from each other, and each independently represent a substituted or unsubstituted C6-C30 aryl group.

In an exemplary embodiment of the present specification, Ar1 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted fluorene group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted fluorene group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted phenyl group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group substituted with one or more selected from the group consisting of a halogen group and an alkyl group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group substituted with a halogen group.

In an exemplary embodiment of the present specification, Ar5 is a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, Ar5 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Ar5 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted fluorene group.

In an exemplary embodiment of the present specification, Ar5 is a substituted or unsubstituted fluorene group.

In an exemplary embodiment of the present specification, Ar5 is a fluorene group substituted with one or more selected from the group consisting of an alkyl group, an aryl group, and a curing group.

In an exemplary embodiment of the present specification, Ar5 is a substituted or unsubstituted 9,9-diphenylfluorenyl group.

In an exemplary embodiment of the present specification, Ar5 is a 9,9-diphenylfluorenyl group unsubstituted or substituted with one or more of an alkyl group and a curing group.

In an exemplary embodiment of the present specification, Chemical Formula 2 is any one of the following structures.

In the structure,

L20 and L21 are the same as or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group,

R10 to R12 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R20 and R21 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a curable group,

a11 and m3 are each an integer from 1 to 5,

a12 is an integer from 1 to 4;

When a11, a12 and m3 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

은 화학식 2에 결합되는 부위이다.

is a site bound to Formula 2;

In an exemplary embodiment of the present specification, L20 is a substituted or unsubstituted arylene group.

In an exemplary embodiment of the present specification, L20 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L20 is a substituted or unsubstituted phenylene group.

In an exemplary embodiment of the present specification, L21 is a substituted or unsubstituted arylene group.

In an exemplary embodiment of the present specification, L21 is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In the exemplary embodiment of the present specification, L21 is a substituted or unsubstituted biphenylene group.

In an exemplary embodiment of the present specification, Chemical Formula 2 is any one of the following structures.

In the structure,

R10 to R15 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R20 and R21 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a curable group.

a11 and m3 are each an integer from 1 to 5,

a12 to a15 are each an integer of 1 to 4,

When a11 to a15 and m3 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

은 화학식 2에 결합되는 부위이다.

is a site bound to Formula 2;

In an exemplary embodiment of the present specification, R11 to R15 are the same as or different from each other, and each independently hydrogen; or a halogen group.

In an exemplary embodiment of the present specification, R11 is hydrogen; or a halogen group.

In an exemplary embodiment of the present specification, R11 is hydrogen; or F.

In an exemplary embodiment of the present specification, R12 to R15 are each hydrogen.

In an exemplary embodiment of the present specification, R20 and R21 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; or a curable group.

In an exemplary embodiment of the present specification, R20 and R21 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; or a curable group.

In an exemplary embodiment of the present specification, R20 and R21 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with an alkyl group; or a curable group.

In an exemplary embodiment of the present specification, R20 and R21 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group; or a curable group.

In an exemplary embodiment of the present specification, Chemical Formula 2 is any one of the following structures.

In the exemplary embodiment of the present specification, Ra to Rd are the same as each other.

In an exemplary embodiment of the present specification, X is C; Si; Or a substituted or unsubstituted adamantyl group.

In an exemplary embodiment of the present specification, X is C; Si; or an adamantyl group.

In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

L1, L2, Y1, Ar1, R1 to R3, n1, m1, and m2 are as defined in Formula 2.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 1-2 or 1-3.

[Formula 1-2]

[Formula 1-3]

In Formulas 1-2 and 1-3,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

m1, m2, Ar1, L2, Y1 and R1 to R3 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formulas 1-4 or 1-5.

[Formula 1-4]

[Formula 1-5]

In Formulas 1-4 and 1-5,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

m1, m2, Ar1, L2, Y1 and R1 to R3 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formulas 1-6 or 1-7.

[Formula 1-6]

[Formula 1-7]

In Formulas 1-6 and 1-7,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

m1, m2, Ar1 and R1 to R3 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formulas 1-8 or 1-9.

[Formula 1-8]

[Formula 1-9]

In Formulas 1-8 and 1-9,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

m1, m2, Ar1 and R1 to R3 are as defined in Formula 2 above,

L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

L6 is a substituted or unsubstituted arylene group,

Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R10 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

m3 is an integer from 1 to 5,

When m3 is 2 or more, R10 of 2 or more are the same as or different from each other

In an exemplary embodiment of the present specification, the compound of Formula 1 is represented by any one of the following structures.

In the above structure, t-Bu is a tert-butyl group.

The compound according to an exemplary embodiment of the present specification may have a core structure as shown in Scheme 1 below. In addition, the substituents may be combined by a method known in the art, and the type, position or number of the substituents may be changed according to a method known in the art.

<Scheme 1>

In the above reaction formula,

X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,

L1, L2, Y1, Ar1, R1 to R3, n1, m1 and m2 are the same as defined in Formula 2.

In one embodiment of the present specification, there is provided a coating composition comprising the compound of Formula 1 described above.

In an exemplary embodiment of the present specification, the coating composition includes the compound of Formula 1 and a solvent.

In one embodiment of the present specification, the coating composition may be in a liquid state. The "liquid phase" means a liquid state at room temperature and pressure.

In one embodiment of the present specification, the solvent is, for example, a chlorine-based solvent such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, Isophorone, Tetralone, Decalone, and Acetylacetone; ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalents such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, and 1,2-hexanediol alcohols and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; A solvent such as tetralin is exemplified, but any solvent capable of dissolving or dispersing the compound of Formula 1 according to an exemplary embodiment of the present invention is sufficient, and the present invention is not limited thereto.

In another exemplary embodiment, the solvent may be used alone or as a mixture of two or more solvents.

In one embodiment of the present specification, the coating composition does not further include a p-doping material.

In one embodiment of the present specification, the coating composition further comprises a p-doping material.

In the present specification, the p-doped material refers to a material that allows the host material to have p-semiconductor properties. The p-semiconductor property refers to the property of receiving or transporting holes at the highest occupied molecular orbital (HOMO) energy level, that is, the property of a material having high hole conductivity.

In the exemplary embodiment of the present specification, the p-doping material may be represented by any one of the following Chemical Formulas A to H, but is not limited thereto.

[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

[Formula F]

[Formula G]

[Formula H]

In the present specification, the p-doping material is sufficient as long as it has a p-semiconductor characteristic, and one or two or more types may be used, and the type thereof is not limited.

In an exemplary embodiment of the present specification, the content of the p-doping material is 0 wt% to 500 wt% based on the compound of Formula 1 above. Specifically, the content of the p-doping material is 100 wt% to 400 wt% based on the compound of Formula 1 above.

In an exemplary embodiment of the present specification, the content of the p doping material includes 0 to 50% by weight based on the total solid content of the coating composition. In an exemplary embodiment of the present specification, the content of the p doping material is preferably 1 to 50% by weight based on the total solid content of the coating composition, and in another exemplary embodiment, the p doping material The content of is more preferably 10 to 30% by weight based on the total solid content of the coating composition.

In another embodiment, the coating composition is a single molecule comprising a functional group that can be crosslinked by heat or light; Alternatively, it may further include a single molecule including a terminal group capable of forming a polymer by heat. a single molecule including a functional group that can be crosslinked by heat or light as described above; Alternatively, the molecular weight of a single molecule including a terminal group capable of forming a polymer by heat may be a compound of 3,000 g/mol or less.

In an exemplary embodiment of the present specification, the coating composition has a molecular weight of 2,000 g/mol or less, and a single molecule including a functional group that can be crosslinked by heat or light; Or it further includes a monomolecular containing a terminal group capable of forming a polymer by heat.

a single molecule including a functional group crosslinkable by the heat or light; Alternatively, a single molecule including a terminal group capable of forming a polymer by heat may be aryl such as phenyl, biphenyl, fluorene, or naphthalene; arylamine; Alternatively, it may refer to a single molecule in which fluorene is substituted with a functional group crosslinkable by heat or light or a terminal group capable of forming a polymer by heat.

In another exemplary embodiment, the viscosity of the coating composition is 2 cP to 15 cP at room temperature. When the above viscosity is satisfied, it is easy to manufacture a device.

The present specification also provides an organic light emitting device formed using the coating composition.

In one embodiment of the present specification, the first electrode; a second electrode; and at least one organic material layer including a light emitting layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the coating composition or a cured product thereof. In this case, the cured product of the coating composition is in a state in which the coating composition is cured by heat treatment or light treatment.

In an exemplary embodiment of the present specification, the organic material layer including the coating composition or a cured product thereof is a hole transport layer or a hole injection layer.

In an exemplary embodiment of the present specification, the organic material layer including the coating composition or a cured product thereof is an electron transport layer or an electron injection layer.

In another embodiment, the organic material layer including the coating composition or a cured product thereof is a light emitting layer.

In another exemplary embodiment, the organic material layer including the coating composition or a cured product thereof is a light emitting layer, and the light emitting layer includes the compound of Formula 1 as a host of the light emitting layer.

In another exemplary embodiment, the organic material layer including the coating composition or a cured product thereof is a light emitting layer, and the light emitting layer includes the compound of Formula 1 as a dopant of the light emitting layer.

In an exemplary embodiment of the present specification, the organic light emitting device includes a hole injection layer and a hole transport layer. It further comprises one or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, a layer that simultaneously transports and injects holes, and a layer that simultaneously transports and injects electrons. .

In the exemplary embodiment of the present specification, 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.

In another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In another exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

The organic material layer of the organic light emitting device of the present specification 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 of the present invention includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a layer for performing hole transport and hole injection at the same time, and a layer for simultaneously performing electron transport and electron injection as an organic material layer. can have a structure. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

For example, the structure of the organic light emitting diode according to an exemplary embodiment of the present specification is illustrated in FIGS. 3 and 4 .

3 illustrates a structure of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked.

4 shows organic light emitting diodes in which a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron injection and transport layer 7 and a cathode 4 are sequentially stacked. The structure of the device is illustrated.

3 and 4 illustrate an organic light emitting device, the structure of the organic light emitting device of the present invention is not limited thereto.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present invention may be stacked in a structure as illustrated in the following example.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer is formed using a coating composition including the compound of Formula 1 above.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and then formed thereon through a hole injection layer, a hole transport layer, a light emitting layer, and an organic material layer solution process including a layer that simultaneously transports and injects electrons, a deposition process, etc., and then deposited thereon with a material that can be used as a cathode can be 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 present specification also provides a method of manufacturing an organic light emitting device formed using the coating composition.

Specifically, one embodiment of the present specification includes the steps of preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer includes forming one or more organic material layers using the coating composition.

In one embodiment of the present specification, the step of forming one or more organic material layers using the coating composition uses a spin coating method.

In another embodiment, the step of forming one or more organic material layers using the coating composition uses a printing method.

In the present specification, the printing method includes, for example, inkjet printing, nozzle printing, offset printing, transfer printing, or screen printing, but is not limited thereto.

Since the coating composition according to an exemplary embodiment of the present specification is suitable for a solution process due to its structural characteristics, it can be formed by a printing method, so that there is an economical effect in time and cost in manufacturing the device.

In one embodiment of the present specification, the step of forming one or more organic material layers using the coating composition comprises: coating the coating composition on the first electrode or one or more organic material layers; and heat-treating or light-treating the coated coating composition.

In an exemplary embodiment of the present specification, the heat treatment may be performed through heat treatment, and the heat treatment temperature in the heat treatment step may be 85° C. to 250° C., and 100° C. to 250° C. according to an exemplary embodiment, In another exemplary embodiment, it may be 150 °C to 250 °C.

In another exemplary embodiment, the heat treatment time in the heat treatment step is 1 minute to 2 hours, according to an exemplary embodiment, may be 1 minute to 1 hour, in another exemplary embodiment, 30 minutes to It can be 1 hour.

In the step of coating the coating composition on the first electrode or one or more organic material layers, a solvent that does not dissolve the material of the lower layer is used. For example, when the coating composition is applied to the hole transport layer, the coating composition includes a solvent that does not dissolve the material of the lower layer (first electrode, hole injection layer, etc.). Accordingly, there is an advantage that the hole transport layer can be introduced through a solution process.

Through the step of heat-treating or light-treating the coated coating composition, a plurality of the compounds included in the coating composition form a cross-link to provide an organic material layer including a thinned structure. In this case, when another layer is laminated on the surface of the organic material layer formed by using the coating composition, it can be prevented from being dissolved, morphologically affected, or decomposed by a solvent.

Therefore, when the organic material layer formed by using the coating composition is formed including a heat treatment or light treatment step, resistance to solvent increases, so that a multilayer can be formed by repeatedly performing solution deposition and crosslinking methods, and stability of the device is increased Lifespan characteristics can be increased.

As the anode material, a material having a large work function is generally preferred 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 invention 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 : a combination of a metal such as Sb and an oxide; 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 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 barium, 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 for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include the compound of Formula 1, metal porphyrin, oligothiophene, an arylamine-based organic material, a hexanitrile hexaazatriphenylene-based organic material, and a quinacridone-based organic material. , perylene-based organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. material is suitable. Specifically, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. More specifically, the hole transport layer may be a compound containing an arylamine group.

The layer for performing hole transport and hole injection at the same time may include materials of the aforementioned hole transport layer and hole injection layer.

The light emitting material included in the light emitting layer 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.

The emission layer may include a host material and a dopant material. The host material may be 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, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. More specifically, an anthracene derivative may be used as the host.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto. More specifically, as the dopant, a compound including an arylamine group substituted with a silyl group may be used.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons as an electron injection material, has an electron injection effect from the cathode, has an excellent electron injection effect on the light emitting layer or the light emitting material, and is generated in the light emitting layer A compound which prevents the exciton from moving to the hole injection layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, benzimidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

The layer for simultaneously transporting and injecting electrons may include the materials of the electron transport layer and the electron injection layer described above.

Specifically, the electron injection and transport layer includes a benzimidazole group.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, 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-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

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

The electron blocking layer is a layer that blocks electrons from reaching the anode, and a material known in the art may be used.

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

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

Synthesis example 1. Preparation of compound 1

(1) Preparation of compound K-1

Starting material (2-bromo-9-(2,5-dimethylphenyl)-9-(4-vinylphenyl)-9H-fluorene) 10 g (22.1528 mmol), aniline 4216 mg (44.3056 mmol) , sodium tert-butoxide (NaOt-Bu) 6386 mg (66.4584 mmol) and 110 ml of toluene were added to the flask, and nitrogen was bubbled for 30 minutes. 340 mg (0.6646 mmol) of bis(tri-tert-butylphosphine)palladium(0)(Pd(Pt-bu ₃ ) ₂ ) was added to a flask and stirred at 90° C. overnight. When the reaction was completed, it was cooled to room temperature and 100 ml of water was added thereto. After extraction with ethyl acetate (EA) three times, the organic layers were collected, dried over magnesium sulfate (MgSO ₄ ), and filtered. The organic solvent was removed and column purification was performed with 20% ethyl acetate/hexane (EA/Hex). Drying gave 7.6 g of compound K-1.

(2) Preparation of compound 1

Tetrakis (4'-bromo- [1,1'-biphenyl] -4-yl) methane 3212 mg (3.4151 mmol), compound K-1 7,600 mg (16.3927 mmol), NaOt-Bu 4594 mg (47.8122) mmol) and 80 ml of toluene were added to the flask, and nitrogen was bubbled for 30 minutes. Pd(Pt-Bu ₃ ) ₂ 209 mg (0.4098 mmol) was added to a flask and stirred at 90° C. for 48 hours. Upon completion of the reaction, the flask was cooled to room temperature, and 80 ml of water was added to terminate the reaction. The organic layer was collected by extraction with EA 3 times, treated with MgSO ₄ , and filtered to obtain an organic layer. The solvent of the organic layer was removed and purified by 30% EA/Hex column to obtain 4.1 g of Compound 1.

5 shows the NMR measurement result of Compound 1.

m/z: 2471.15 (100.0%), 2470.14 (98.4%), 2469.14 (48.1%), 2472.15 (42.3%), 2473.15 (33.9%), 2472.15 (25.1%), 2474.16 (8.5%), 2474.16 (5.1%) ), 2475.16 (3.0%), 2472.15 (1.7%), 2471.15 (1.6%), 2472.14 (1.5%), 2475.16 (1.5%), 2471.14 (1.5%), 2476.16 (1.0%)

Synthesis example 2. Preparation of compound 2

Tetrakis (4'-bromo- [1,1'-biphenyl] -4-yl) silane 2,579 mg (2.6962 mmol), compound K-1 6,000 mg (12.9416 mmol), NaOt-Bu 3,886 mg (40.4430) mmol) and 65 ml of toluene were added to the flask and nitrogen was bubbled for 30 minutes. Pd(Pt-Bu ₃ ) ₂ 165 mg (0.3235 mmol) was added to the flask and stirred at 90° C. for 48 hours. After the reaction was completed, the flask was cooled to room temperature, and 65 ml of water was added to terminate the reaction. The organic layer was collected by extraction with EA 3 times, treated with MgSO ₄ , and filtered to obtain an organic layer. The solvent of the organic layer was removed and purified by 30% EA/Hex column to obtain 3.2 g of Compound 2.

Synthesis example 3. Preparation of compound 3

(1) Preparation of compound K-2

Compound K-1 was prepared in the same manner as in Synthesis Example 1 (1). Compound K-1 5,000 mg (10.7847 mmol), 1-bromo-4-iodobenzene (1-bromo-4-iodobenzene) 4,576 mg (16.1770 mmol), NaOt-Bu 1,555 mg (16.1770 mmol) and toluene 54 ml was put into the flask and nitrogen was bubbled for 30 minutes. Tris(dibenzylideneacetone)dipalladium(0)(Pd ₂ (dba) ₃ ) 198 mg (0.2157 mmol) and tri-tert-butylphosphine (Pt-Bu ₃ ) 44 mg (0.2157 mmol) were added to a flask and stirred at 80 °C for 4 hours. Upon completion of the reaction, the flask was cooled to room temperature, and 54 ml of water was added to terminate the reaction. The organic layer was collected by extraction with EA 3 times, treated with MgSO ₄ , and filtered to obtain an organic layer. The solvent of the organic layer was removed and purified by 20 % EA/Hex column to obtain 4.7 g of compound K-2.

(2) Preparation of compound 3

1,3,5,7-tetrakis(4-(4,4,5,5-tetramethyl-1,3,2-dioxyborolanyl-2-yl)phenyl)amamantane 1,495 mg (1.5828) mmol), compound K-2 4,700 mg (7.5976 mmol), potassium carbonate (K ₂ CO ₃ ) 1,750 mg (12.6624 mmol), tetrahydrofuran (THF) 15 ml and water 7 ml were placed in a flask and nitrogen for 30 minutes bubbled. Tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ ) 219 mg (0.1899 mmol) was added to a flask and stirred at 90° C. for 48 hours. Upon completion of the reaction, the flask was cooled to room temperature, and 20 ml of water was added to terminate the reaction. The organic layer was collected by extraction with EA 3 times, treated with MgSO ₄ , and filtered to obtain an organic layer. The solvent of the organic layer was removed and purified by 20% EA/Hex column to obtain 1.4 g of Compound 3.

Synthesis example 4. Preparation of comparative compound W1

(1) Preparation of compound W-1

10 g (22.7583 mmol) of the starting material, 4,239 mg (45.5166 mmol) of aniline, 6,561 mg (68.2749 mmol) of NaOt-Bu and 110 ml of toluene were added to a flask and nitrogen was bubbled for 30 minutes. Pd(Pt-Bu ₃ ) ₂ 349 mg (0.6827 mmol) was added to the flask and stirred at 90° C. for 4 hours. Upon completion of the reaction, the flask was cooled to room temperature, and 110 ml of water was added to terminate the reaction. The organic layer was collected by extraction with EA 3 times, treated with MgSO ₄ , and filtered to obtain an organic layer. The solvent of the organic layer was removed and purified by 10% EA/Hex column to obtain 8.2 g of compound W-1.

(2) Preparation of comparative compound W1

Tetrakis (4'-bromo-[1,1'-biphenyl]-4-yl) methane 3,557 mg (3.7828 mmol), compound C 8,200 mg (18.1573 mmol), NaOt-Bu 5,453 mg (56.742 mmol) and 90 ml of toluene were added to the flask, followed by nitrogen bubbling for 30 minutes. Pd(Pt-Bu ₃ ) ₂ 232 mg (0.4539 mmol) was added to the flask and stirred at 90° C. for 48 hours. Upon completion of the reaction, the flask was cooled to room temperature, and 90 ml of water was added to terminate the reaction. The organic layer was collected by extraction with EA 3 times, treated with MgSO ₄ , and filtered to obtain an organic layer. The solvent of the organic layer was removed and purified by 50 % MC/Hex column to obtain 6 5 g of comparative compound W1.

Example One.

Step 1) Preparation of coating composition

A coating composition was prepared by mixing Compound 1 prepared in Synthesis Example 1 above, a material of Formula D below, and cyclohexanone as a solvent in a weight ratio of 2:8:490.

[Formula D]

Step 2) Fabrication of an organic light emitting device

A glass substrate on which indium tin oxide (ITO) was deposited to a thickness of 1500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing with a solvent of isopropyl alcohol and acetone was performed for 30 minutes each and dried, and then the substrate was transported to a glove box.

On the thus prepared ITO transparent electrode, the coating composition prepared in step 1 was spin-coated to form a hole injection layer having a thickness of 300 Å, and the coating composition was cured on a hot plate under a nitrogen atmosphere for 30 minutes. Thereafter, after transferring to a vacuum evaporator, the following compound Z-1 was vacuum-deposited to a thickness of 1000 Å on the hole injection layer to form a hole transport layer. On the hole transport layer, the following compound Z-2 and the following compound Z-3 were vacuum-deposited to a thickness of 300 Å in a weight ratio of 92:8 to form a light emitting layer. On the light emitting layer, the following compound Z-4 was vacuum deposited to a thickness of 200 Å to form an electron injection and transport layer. A cathode was formed by sequentially depositing LiF to a thickness of 12 Å and aluminum to a thickness of 2000 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 0.3 Å/sec for LiF and 2 Å/sec for aluminum was maintained, and the vacuum degree during deposition was 2x10 ^-7 torr to 5x10 ^-8 torr was maintained.

Example 2 and 3.

In Example 1, an organic light emitting device was manufactured in the same manner as in Example 1, except that the materials of Table 1 below were used instead of the materials of Compound 1 and Formula D when preparing the coating composition.

comparative example 1 and 2

In Example 1, an organic light emitting device was manufactured in the same manner as in Example 1, except that the materials of Table 1 below were used instead of the materials of Compound 1 and Formula D when preparing the coating composition.

The structures of Comparative Compounds W1 and W2 used in Comparative Examples 1 and 2 are as follows, respectively.

Materials of Formula F used in Example 3, Comparative Example 1 and Comparative Example 2 are as follows.

[Formula F]

By applying a current to the organic light emitting devices prepared in Examples 1 to 3 and Comparative Examples 1 and 2, driving voltage, current efficiency, power efficiency, and lifetime (T95) were measured, and the results are shown in Table 1 below. T95 in Table 1 below means the time measured until the initial luminance is lowered to 95%.

hole
injection layer doping material drive voltage
(V)
(@10 mA/cm ² ) current efficiency
(cd/A)
(@10 mA/cm ² ) power efficiency
(lm/W)
(@10 mA/cm ² ) LT95
(hr)
(@10 mA/cm ² ) Example 1 compound 1 Formula D 5.2 7.98 4.82 49 Example 2 compound 2 Formula D 5.00 7.93 4.98 30 Example 3 compound 3 Formula F 4.97 7.69 4.86 41 Comparative Example 1 compare
compound W1 Formula F 6.50 5.01 2.42 14 Comparative Example 2 compare
compound W2 Formula F 6.90 7.60 3.46 8

From Table 1, it can be seen that the compound of the present invention exhibits excellent performance when applied to the hole injection layer. Specifically, it can be confirmed that the compound of the present invention has excellent solubility in organic solvents, so it is suitable for a solution process, it is easy to prepare a coating composition, and a uniform coating layer can be formed by using the coating composition.

In addition, since the compound of the present invention includes a curing group, the coating layer including the cured product of the coating composition is not dissolved in a solvent when an additional layer is formed on the coating layer, and retaining power is improved. Accordingly, compared to the organic light-emitting device to which the host of the conventional hole injection layer (comparative compound W1) is applied, it prevents the deterioration of the lifespan due to the inflow of the compound between layers, so it can be confirmed that the performance and lifespan of the device are improved compared to Comparative Example 1. can

In addition, it can be confirmed that the performance and lifespan of the device are improved than in Comparative Example 2 by having a packing structure in three dimensions compared to the compound having a linear structure (comparative compound W2).

In addition, when C and Si of the group 14 elements were introduced as X of Formula 1 (Examples 1 and 2), similar performance was shown, so that similar performance was obtained when Ge or Sn, which is an element of the same group, was introduced as X. can be predicted to represent

1: substrate
2: Anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: Electron injection and transport layer

Claims (11)

A compound of formula (1):
[Formula 1]

In Formula 1,
X is C; Si; Ge; Sn; Or a substituted or unsubstituted adamantyl group,
Ra to Rd are the same as or different from each other, and are each independently represented by the following formula (2),
[Formula 2]

In Formula 2,
L1 is a direct bond; a substituted or unsubstituted arylene group; or -L3-N(Ar2)-;
L2 is a direct bond; Or a substituted or unsubstituted arylene group,
L3 is a substituted or unsubstituted arylene group,
Y1 is a curing group,
Ar1, Ar2, and R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
n1 is an integer from 1 to 5,
m1 is an integer from 1 to 3,
m2 is an integer from 1 to 4,
When n1 is 2 or more, L1 of 2 or more are the same as or different from each other,
When m1 and m2 are each 2 or more, the substituents in parentheses are the same as or different from each other,

is a site bound to Formula 1. The method according to claim 1,
Wherein Ar1 and Ar2 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group. The method according to claim 1,
The curing group is a compound of any one of the following structures:

In the structure,
L10 to L13 are the same as or different from each other, and each independently a direct bond; -O-; Or a substituted or unsubstituted alkylene group,

is a site bound to Formula 2; The method according to claim 1,
Formula 2 is a compound represented by the following Formula 2-1 or 2-2:
[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,
m1, m2, Ar1, L2, Y1 and R1 to R3 are as defined in Formula 2 above,
L5 and L7 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,
L6 is a substituted or unsubstituted arylene group,
Ar5 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group. The method according to claim 1,
The compound of Formula 1 is represented by any one of the following structures:

In the above structure, t-Bu is a tert-butyl group. A coating composition comprising a compound according to any one of claims 1 to 5. a first electrode;
a second electrode; and
At least one organic material layer including a light emitting layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising the coating composition of claim 6 or a cured product thereof. 8. The method of claim 7,
The organic material layer comprising the coating composition or a cured product thereof is an organic light emitting device that is a hole transport layer or a hole injection layer. 8. The method of claim 7,
The organic material layer including the coating composition or a cured product thereof is an organic light emitting device that is a light emitting layer. preparing a substrate;
forming a first electrode on the substrate;
forming one or more organic material layers on the first electrode; and
Forming a second electrode on the organic material layer,
The step of forming the organic material layer is a method of manufacturing an organic light emitting device comprising the step of forming one or more organic material layer using the coating composition of claim 6. 11. The method of claim 10,
The step of forming one or more organic material layers using the coating composition
coating the coating composition on the first electrode or one or more organic material layers; and
Method of manufacturing an organic light-emitting device comprising the step of heat-treating or light-treating the coated coating composition.

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