KR20220026299A - Novel 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 represented by chemical formula 1, a coating composition including a compound represented by chemical formula 1, an organic light emitting element using the same, and a manufacturing method thereof. According to the present invention, a solution process is possible, so that the element can be enlarged.

Description

A novel compound, a coating composition comprising the same, an organic light emitting device using the same, and a manufacturing method thereof {NOVEL COMPOUND, COATING COMPOSITION COMPRISING SAME, ORGANIC LIGHT EMITTING DEVICE USING SAME AND METHOD OF MANUFACTURING SAME}

The present specification relates to a novel 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, if a current is applied between the two electrodes, electrons and holes are respectively injected into the organic material layer from the cathode and the anode. Electrons and holes injected into the organic material 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 generally include a cathode, an anode, and an organic material layer disposed therebetween, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer.

Conventionally, a deposition process has been mainly used to manufacture an organic light emitting device. However, there are problems in that a lot of material loss occurs and it is difficult to manufacture a device having a large area when manufacturing an organic light emitting device through the deposition process. To solve these problems, a device using a solution process is being developed.

Accordingly, there is a demand for development of materials for solution processing.

Korean Patent Publication No. 10-2000-0051826

An object of the present specification is to provide a novel compound and an organic light emitting device including the same.

A compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1,

R1 to R11 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. is a flag,

Ar1 and Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,

n1 to n7 are each an integer from 0 to 4, n8 and n9 are each an integer from 0 to 5, n10 and n11 are each an integer from 0 to 7, and when n1 to n11 are each 2 or more, 2 or more substituents in parentheses are the same or different from each other.

The present specification provides a coating composition comprising the compound.

The present specification also includes a first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more of the one or more organic material layers provides an organic light emitting device including the above-described coating composition or a cured product thereof.

Finally, the present specification includes the steps of preparing a first electrode; forming one or more organic material layers on the first electrode; and forming a second electrode on the one or more organic material layers, wherein the forming of the one or more organic material layers includes forming one or more organic material layers using the coating composition. A method of manufacturing a device is provided.

The compound of Formula 1 of the present invention can be used as a material for an organic material layer of an organic light emitting device, and when applied to a device, a device having a low driving voltage, excellent luminous efficiency and lifespan characteristics can be obtained, and a solution process is possible, which makes the device large area is possible.

According to an exemplary embodiment of the present invention, when the organic material layer of the organic light emitting device is formed by using the coating composition comprising Formula 1, the polymer is formed due to the curable group in the compound, so that the curable group is not bound to the monomolecular compound. Compared to that, there is an advantage in that the coating property is excellent.

In addition, when the organic material layer containing the compound of Formula 1 of the present invention is formed through a solution process and then the organic material layer of the upper layer is formed through a solution process, the organic layer containing the compound of Formula 1 does not dissolve in the solution process solvent of the upper layer, so the device The advantage is that the performance of the

1 illustrates an example of an organic light emitting device according to an exemplary embodiment of the present specification.
2 is a diagram showing NMR data of Compound 1-2.
3 is a diagram showing NMR data of compound 1-3.
4 is a diagram showing NMR data of Compound 1.

Hereinafter, the present specification will be described in detail.

In the present specification, when a member (layer) is said to be located “on” another member (layer), this is not only when a member (layer) is in contact with another member but also between two members (layers). (layer) is also included.

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 “curable group” refers to a photocurable group or a thermosetting group, and may refer to a reactive substituent for crosslinking 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.

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

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

As used herein, the term "substituted or unsubstituted" is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a nitrile group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, and a heteroaryl group, It means that it is unsubstituted or substituted with a substituent to which two or more substituents are connected among the above-exemplified 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, and may be interpreted as a substituent in which two phenyl groups are connected.

In addition, as used herein, the term “substituted or unsubstituted” refers to at least one selected from the group consisting of deuterium, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, and a heteroaryl group having 2 to 60 carbon atoms. It means that it is unsubstituted or substituted with a substituent, or substituted or unsubstituted with a substituent to which two or more of the above-exemplified substituents are connected.

In the present specification, the halogen group is a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br) or an iodo group (-I).

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

In the present specification, the cycloalkyl group is not particularly limited, but may have 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group may have 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. 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, a cyclooctyl group, and the like.

In the present specification, the alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but may be 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, n-no It may be a nyloxy group, an n-decyloxy group, etc., but is not limited thereto.

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 triphenylenyl 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

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

In the present specification, the heteroaryl group is an aromatic ring group including at least one of N, O, P, S, Si and Se as a heteroatom, and the number of carbon atoms is not particularly limited, but may be from 2 to 60 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 2 to 30 carbon atoms. Examples of the heteroaryl group include a pyridine group, a pyrrole group, a pyrimidine group, a pyridazine group, a furan group, a thiophene group, a benzothiophene group, a benzofuran group, a dibenzothiophene group, a dibenzofuran group, and the like. However, the present invention is not limited thereto.

The present specification provides a compound represented by Formula 1 above.

In an exemplary embodiment of the present specification, the compound of Formula 1 is preferably a compound having solubility in a suitable organic 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 compound of Formula 1, terphenylene is bonded as a linker between two amines, thereby increasing conjugation in the compound to control the energy level. This has the advantage of facilitating the movement of holes.

According to an exemplary embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _{1 - 20} is an alkoxy group, a substituted or unsubstituted C _6-30 aryl group, or a substituted or unsubstituted C _2-30 heteroaryl group.

In another exemplary embodiment, R1 to R3 are the same as or different from each other, and each independently represent hydrogen or a substituted or unsubstituted C _1-20 alkyl group.

In another exemplary embodiment, R1 to R3 are the same as or different from each other, and each independently represents hydrogen or a substituted or unsubstituted hexyl group.

In another exemplary embodiment, R1 to R3 are the same as or different from each other, and each independently represents a hydrogen or a hexyl group.

According to an exemplary embodiment of the present specification, each of the n1 to n3 is an integer of 0 to 2, and when n1 to n3 are each 2, the substituents in the two parentheses are the same as or different from each other.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2,

R1, R3 to R11, n1, n3 to n11, Ar1 and Ar2 have the same definitions as in Formula 1,

R21 and R22 are the same as or different from each other and each independently represent a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R21 and R22 are the same as or different from each other, and each independently represents a substituted or unsubstituted C _1-20 alkyl group.

According to another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently represent a substituted or unsubstituted hexyl group.

According to another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently represents a hexyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted C _6-30 aryl group or a substituted or unsubstituted C _2-30 heteroaryl group .

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently represent an aryl group unsubstituted or substituted with one or more halogen groups.

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently represent a C _6-30 aryl group unsubstituted or substituted with one or more halogen groups.

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently represents a C _6-30 aryl group unsubstituted or substituted with one or more fluoro groups.

In another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group.

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group substituted or unsubstituted with one or more halogen groups, a biphenyl group unsubstituted or substituted with one or more halogen groups, or one or more halogen groups. It is a terphenyl group unsubstituted or substituted with a group.

According to another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with one or more fluoro groups, a biphenyl group unsubstituted or substituted with one or more fluoro groups, or 1 It is a terphenyl group unsubstituted or substituted with the above fluoro group.

In an exemplary embodiment of the present specification, Formula 1 is represented by Formula 3 below.

[Formula 3]

In Formula 3,

Definitions of R1 to R11, n1 to n11, Ar1 and Ar2 are the same as in Formula 1.

According to an exemplary embodiment of the present specification, R4 to R11 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _{1 - 20} is an alkoxy group, a substituted or unsubstituted C _6-30 aryl group, or a substituted or unsubstituted C _2-30 heteroaryl group.

According to an exemplary embodiment of the present specification, R4 to R7, R10 and R11 are each hydrogen.

According to an exemplary embodiment of the present specification, R8 and R9 are the same as or different from each other, and each independently represents a substituted or unsubstituted C _1-20 alkyl group. When R8 and R9 are an alkyl group, the solubility of the compound of Formula 1 is increased and a side reaction of the reaction intermediate is prevented when the organic layer is formed.

According to an exemplary embodiment of the present specification, R8 and R9 are the same as or different from each other, and each independently represents a substituted or unsubstituted methyl group.

According to an exemplary embodiment of the present specification, R8 and R9 are each a methyl group.

According to an exemplary embodiment of the present specification, n4 to n11 are each an integer of 0 to 2, and when n4 to n11 are each 2, the substituents in the two parentheses are the same as or different from each other.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 4 below.

[Formula 4]

In Formula 4,

R1, R3 to R7, R10, R11, n1, n3 to n7, n10, n11, Ar1 and Ar2 have the same definitions as in Formula 1,

R21 and R22 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group,

R31 to R34 are the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, R31 to R34 are the same as or different from each other, and each independently represents a substituted or unsubstituted C _1-20 alkyl group.

According to another exemplary embodiment, R31 to R34 are the same as or different from each other, and each independently represent a substituted or unsubstituted methyl group.

In another exemplary embodiment, R31 to R34 are each a methyl group.

In an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following compounds.

According to an exemplary embodiment of the present specification, the compound of Formula 1 may have a core structure as in Preparation Examples to be described later. 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.

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 content of the p-doping material is 0 wt% to 50 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 30% 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 30% by weight based on the total solid content of the coating composition, and in another exemplary embodiment, the p doping material The content of the coating composition more preferably includes 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 photocurable group and / or thermosetting group; Alternatively, it may further include a single molecule including a terminal group capable of forming a polymer by heat. Monomolecules containing a photocurable group and/or a thermosetting group 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.

a single molecule comprising the photocurable group and/or the thermosetting group; 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 a photocurable group and/or a thermosetting group or a terminal group capable of forming a polymer by heat is substituted with fluorene.

In another exemplary embodiment, the viscosity of the coating composition is 1 cP to 20 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 provided between the first electrode and the second electrode, wherein at least one organic material layer of the at least one layer contains the coating composition or a cured product thereof, and the cured product of the coating composition is the The coating composition is in a cured state 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 exemplary 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 an emission layer, and the emission layer includes the compound of Formula 1 as a host of the emission 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 includes 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 hole injection and transport layer, and an electron transport and injection layer.

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 may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole injection and transport layer, an electron injection and transport layer, etc. as an organic material layer. 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 device according to an exemplary embodiment of the present specification is illustrated in FIG. 1 .

1, a first electrode 201, a hole injection layer 301, a hole transport layer 401, a light emitting layer 501, an electron injection and transport layer 601 and a second electrode 701 are sequentially shown on a substrate 101 The structure of the organic light-emitting device stacked with Here, the electron injection and transport layer means a layer that simultaneously injects and transports electrons. The hole injection layer 301 and/or the hole transport layer 401 of FIG. 1 may be formed using a coating composition including the compound of Formula 1 described above.

1 illustrates an organic light emitting device, but 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 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 an organic material layer including at least one layer of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, an electron transport layer, a hole injection and transport layer, and an electron injection and transport layer thereon. It can be prepared by depositing a material that can be used as a cathode on it. 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, in one embodiment of the present specification, the steps of preparing a first electrode; forming one or more organic material layers on the first electrode; and forming a second electrode on the one or more organic material layers, wherein the forming of the one or more organic material layers 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, thereby having an economical effect in terms of 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 from 60° C. to 250° C., and according to an exemplary embodiment, from 100° C. to 250° C., 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.

When the step of forming one or more organic material layers formed by using the coating composition includes the heat treatment or light treatment step, a plurality of the compounds included in the coating composition form cross-linking to provide an organic material layer including a thinned structure. can In this case, when another layer is laminated on the surface of the organic material layer formed using the coating composition, it can be prevented from being dissolved, morphologically affected, or decomposed by the solvent of the other layer.

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 cathode 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 preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode 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. The hole transport material is a material capable of transporting holes from the anode or hole injection layer to the light emitting layer and has high hole mobility. material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The hole injection and transport layer may include the material of the hole transport layer and/or the hole injection layer described above.

The light emitting material is a material capable of emitting light in the visible ray region by transporting 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 includes 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.

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, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted in the arylamine, 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, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. Do. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may 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 a layer of aluminum or silver. 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 that prevents the excitons 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, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

The electron injection and transport layer may include the above-described material for the electron transport layer and/or the electron injection layer.

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 be generally 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.

< production example >

production example 1. Preparation of compound 1

One)

Put the compound 1-1 (12g, 27.2mmol) and nitrobenzaldehye (4.52g, 29.9mmol) in a round bottom flask, Cs ₂ CO ₃ (2.437g, 7.48mmol), Cu(OAc) ₂ (247mg, 1.36mmol) After addition, N ₂ was substituted. After addition of dimethylformamide (DMF) (140 mL), the mixture was stirred at 100° C. overnight. After the addition of H ₂ O, the mixture was evaporated and purified by column chromatography to prepare the compound 1-2. At this time, the NMR data of the prepared compound 1-2 are shown in FIG. 2 below.

2)

CH ₃ PPh ₃ Br 2eq and tetrahydrofuran (THF) were added to a round bottom flask and placed in an ice bath. After putting 2eq of KOtBu at O°C and stirring for 20 minutes, compound 1-2 was put into another round bottom flask and dissolved in THF was added by cannula. After 1 hour, H ₂ O was added, quenched, extracted, and purified by column chromatography to prepare compound 1-3. At this time, the NMR data of the prepared compound 1-3 are shown in FIG. 3 below.

3)

Put the compound SM-NH (1.6 g, 2.18 mmol) and compound 1-3 (2.39 g, 4.4 mmol) in a round bottom flask, NaOtBu (629 mg, 6.54 mmol), toluene (40 mL) and Pd (tBu ₃ P) ₂ (5 mol%) was added and stirred at 70° C. for an hour and a half. Then, the compound 1 was prepared by purification by column chromatography. At this time, the NMR data of the prepared compound 1 is shown in FIG. 4 below.

production example 2. Preparation of compound 2

Put the compound SM-NH1 (1.68 g, 2.18 mmol) and compound 1-3 in a round bottom flask, NaOtBu (629 mg, 6.54 mmol), toluene (40 mL) and Pd (tBu ₃ P) ₂ (5 mol%) After the addition, the mixture was stirred at 70° C. for an hour and a half. Then, the compound 2 was prepared by purification by column chromatography.

production example 3. Preparation of P-1

Step 1) Preparation of compound 3-1'

Mg (193 mg, 7.92 mmol), I ₂ (4 mg) and THF (10 mL) were added to a 100 mL round bottom flask under a nitrogen atmosphere and stirred for 30 minutes. 4-Bromostyrene (1.04 mL, 7.92 mmol) was added, and a 30°C water bath was placed under the round bottom flask and stirred for one day. It was confirmed that the reaction solution became black and Mg was dissolved. Ether (5 mL) was added to dilute the reaction solution. Tris(pentafluorophenyl)borane (1 g, 3.96 mmol) was dissolved in ether (5 mL) and slowly added to the reaction solution for 30 minutes. The solution was stirred for one day. Na ₂ CO ₃ (0.1 M, 80 mL, 8.0 mmol) was slowly added to the reaction solution. The organic solvent was extracted using ethyl acetate (20 mL × 3) and the residue was removed with MgSO ₄ . In order to additionally remove residual water and impurities, it was distilled with benzene using Dean-stock. When about 10 mL of the solvent remained, the solution was cooled and filtered to prepare compound 3-1' (1.6 g, yield 64%).

Step 2) Preparation of compound P-1

Compound 3-1' (100 mg, 0.16 mmol), distilled water (10 mL), and Ph ₂ ICl (60 mg, 0.19 mmol) were added to a 25 mL round bottom flask and stirred for 1 hour. Acetone (15 mL) was added to the reaction solution to cause a precipitate, and the precipitate was filtered and dried to prepare compound P-1 (140 mg, yield 100%).

MS: [MH] ^- = 615 (negative mode)

MS: [M+H] ⁺ = 281 (positive mode)

production example 4. Preparation of P-2

Step 1) Preparation of compound 3-2'

Methyltriphenyl potassium bromide (13.90 g, 38.91 mmol) and THF (100 mL) were added to a 250 mL round bottom flask, and the mixture was stirred at 0° C. for 30 minutes. n-BuLi (15.6 mL, 38.91 mmol, 2.5 M in Hexane) was slowly added to the reaction solution and stirred at 0° C. for 30 minutes. To the reaction solution at 0° C., 4-formyl-2,3,5,6-tetrafluoro-1-bromobenzene (5.0 g, 19.47 mmol, in 30 mL THF) was slowly added. The reaction solution was stirred while slowly raising the temperature to room temperature. After 3 hours, ether (100 mL) and a saturated NH ₄ Cl solution (400 mL) were added to the reaction solution. The organic solvent was extracted using ether (200 mL × 2) and the residue was removed with MgSO ₄ . Compound 3-2' (1.29 g, yield 26%) was prepared by column with ethyl acetate:hexane = 1:9 (v:v).

Step 2) Preparation of compound 3-2''

Mg (95 mg, 3.92 mmol), THF (10 mL) and I ₂ (4 mg) were added to a 25 mL round bottom flask and stirred. Compound 3-2' (1.0 g, 3.92 mmol) was added to the reaction solution and stirred at room temperature. After 10 hours, the solution turned black and Mg was completely dissolved, and ether (10 mL) and BCl ₃ (1.3 mL, 1.3 mmol, 1M in hexane solution) were added over 30 minutes. After stirring the reaction solution for one day, Na ₂ CO ₃ (30 mL, 3.0 mmol, 0.1 M in H ₂ O) was added. After extracting the synthetic material with ethyl acetate (10 mL × 3), the residue was removed with MgSO ₄ . After removing all the solvents, water was completely removed using benzene using Dean-stock, and the solid was filtered to prepare compound 3-2'' (340 mg, yield 28%).

Step 3) Preparation of compound P-2

In a 25 mL round bottom flask, compound 3-2'' (200 mg, 0.27 mmol), 1-(4-vinylbenzyl)pyridin-1-ium chloride (69 mg, 0.30 mmol), H ₂ O (10 mL), Methylene chloride (10 mL) was added and stirred vigorously for 30 minutes. The organic solvent was extracted using ether (10 mL × 3) and the residue was removed with MgSO ₄ . The solvent was removed and vacuum dried to prepare compound P-2 (247 mg, yield 100%).

MS: [MH] ^- = 711 (negative mode)

MS: [M+H] ⁺ = 196 (positive mode)

production example 5. Preparation of P-3

Step 1) Preparation of compound 3-3'

In a 50 mL round bottom flask, add 1-bromo-2,3,5,6-tetrafluoro-4-(1,2,2-trifluorovinyl)benzene (2 g, 7.84 mmol) in THF (20 mL) ) and stirred at -78°C for 30 minutes. n-BuLi in hexane (3.45 mL, 8.63 mmol, 2.5 M) was slowly added to the solution and stirred at -78°C for 30 minutes. To the reaction solution was added BCl ₃ (2.6 mL, 2.61 mmol, 1 M in hexanes solution) at -78°C over 15 min. After slowly raising the temperature to room temperature and stirring the reaction solution for one day, water (30 mL) was added. After extracting the synthetic material with ethyl acetate (10 mL × 3), all of the solvent was removed. Benzene was used to completely remove water with Dean-stock, and the solid was filtered to prepare compound 3-3' (800 mg, yield 43%).

Step 2) Preparation of compound P-3

In a 25 mL round-bottom flask, add compound 3-3' (400 mg, 0.56 mmol), diphenyliodonium chloride (176 mg, 0.56 mmol), water (10 mL), and acetone (10 mL), and vigorously 30 stirred for minutes. The solvent was removed by extraction using dichloromethane (10 mL × 3) and dried to prepare compound P-3 (552 mg, yield 100%).

MS: [MH] ^- = 711 (negative mode)

MS: [M+H] ⁺ = 281 (positive mode)

production example 6. Preparation of P-4

Step 1) Preparation of compound 3-4'

Potassium carbonate (10.4 g, 75.3 mmol) was added to a 500 mL round bottom flask, and DMF (200 ml) was added thereto. 2,3,5,6-tetrafluorophenol (10.0 g, 60.22 mmol) was placed in a flask and stirred at 60° C. for 30 minutes. 4-vinylbenzyl chloride (7.66 g, 50.18 mmol) was slowly added to the reaction solution and stirred at 60° C. for 16 hours. Then water (300 mL) and ethyl acetate (200 ml) were added. The organic layer was extracted using ethyl acetate (200 mL × 2), and the residue was removed with MgSO ₄ . Compound 3-4' (11.2 g, yield 79%) was prepared by column with ethyl acetate:hexane = 1:9 (v:v).

Step 2) Preparation of compound 3-4''

Compound 3-4' (10 g, 35.43 mmol) was added to a 250 ml round bottom flask, and ether (130 ml) was added thereto, followed by stirring. The reaction solution was cooled to -78°C and stirred for 30 minutes. n-BuLi (17 ml, 42.52 mmol, 2.5 M in Hexane) was slowly injected over 30 minutes. It was then stirred for 1 hour. BCl ₃ (8.15 ml, 8.15 mmol, 1 M in Hexane) was slowly added over 30 minutes. The reaction solution was slowly heated to room temperature. After stirring the reaction solution for one day, water (200 ml) was added. After extracting the synthetic material with ether (100 mL × 3), all solvents were removed. Thereafter, water was completely removed using benzene using Dean-stock, and the solid was filtered to prepare compound 3-4'' (6.2 g, yield 66%).

Step 3) Preparation of compound P-4

In a 25 mL round-bottom flask, add compound 3-4'' (6.2 g, 5.42 mmol), diphenylidonium chloride (2.57 g, 8.13 mmol), water (50 mL), and acetone (10 mL), and vigorously Stir for 30 minutes. The organic solvent was extracted using methylene chloride (20 mL × 3) and the solvent was removed. Compound P-4 (5.0 g, yield 65%) was prepared by column with methylene chloride:acetone = 9:1 (v:v).

MS: [MH] ^- = 1135 (negative mode)

MS: [M+H] ⁺ = 281 (positive mode)

<Experimental example>

Experimental Example 1.

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, the detergent used was a product of Fischer Co., and the distilled water that had been secondarily filtered was used as the distilled water. 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 cleaning was performed with a solvent of isopropyl alcohol and acetone and dried. After washing the substrate for 5 minutes, the substrate was transported to a glove box.

Spin the 2 wt% cyclohexanone solution containing the host and the dopant in a weight ratio of 8:2 using the compound 1 prepared in Preparation Example 1 as the host and the compound P-1 as the dopant on the ITO transparent electrode prepared as described above. After coating and heat treatment at 230°C for 30 minutes, a hole injection layer having a thickness of 400 Å was formed. A 2 wt% toluene solution of the following a-NPD compound was spin-coated on the hole injection layer and heat-treated at 120° C. for 10 minutes to form a hole transport layer having a thickness of 200 Å.

After transferring to a vacuum evaporator, the following compound A and the following compound B were vacuum-deposited at a weight ratio of 9:1 on the hole transport layer to form a light emitting layer having a thickness of 300 Å. The following compound C was vacuum deposited on the light emitting layer to form an electron injection and transport layer having a thickness of 400 Å. LiF having a thickness of 5 Å and aluminum having a thickness of 1000 Å were sequentially deposited on the electron injection and transport layer to form a cathode.

In the above process, the deposition rate of organic material was maintained at 0.4 ~ 1.0 Å/sec, the deposition rate of LiF of the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-8 ~ 5×10 ^-6 torr was maintained.

Experimental Examples 2 to 6.

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compounds shown in Table 1 were used when the hole injection layer was formed.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

[Compound 6]

Comparative experiment example 1 to 2.

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compounds shown in Table 1 were used when the hole injection layer was formed.

[Comparative compound 1]

[Comparative compound 2]

The driving voltage, luminous efficiency, power efficiency, external quantum efficiency (QE), luminance and color coordinates were measured at a current density of 10 mA/cm ² in the organic light emitting device prepared in the Experimental Examples and Comparative Experimental Examples, and are shown in Table 1 below. it was The external quantum efficiency was calculated as (number of emitted photons)/(number of injected charge carriers), and the color coordinates are x and y coordinates according to the CIE chromaticity diagram (Commission Internationale de L'Eclairage, 1931).

hole injection layer
(host) drive voltage
(V) luminous efficiency
(cd/A) power efficiency
(lm/W) QE
(%) luminance
(cd/m ² ) CIEx CIEy Experimental Example 1 compound 1/ dopant P-3 5.13 4.45 2.72 5.46 466 0.138 0.105 Experimental Example 2 compound 2/ dopant P-4 5.01 4.68 2.93 5.45 468 0.137 0.105 Experimental Example 3 compound 3/ dopant P-2 5.00 4.65 2.92 5.69 478 0.137 0.106 Experimental Example 4 compound 4/ dopant P-1 4.80 4.7 3.07 5.43 462 0.137 0.110 Experimental Example 5 compound 5/ dopant P-1 4.99 4.68 2.94 5.66 468 0.138 0.105 Experimental Example 6 compound 6/ dopant P-2 4.78 4.72 3.10 5.38 455 0.139 0.100 Comparative Experimental Example 1 Comparative compound 1/ dopant P-3 5.54 4.20 2.38 3.12 420 0.137 0.106 Comparative Experimental Example 2 Comparative compound 2/ dopant P-4 5.33 4.28 2.52 3.23 428 0.137 0.106

From the experimental results in Table 1, it can be confirmed that Experimental Examples 1 to 6, which are organic light emitting devices of the present invention, have superior device characteristics than Comparative Experimental Examples 1 and 2. Comparative Experimental Example 1 used Comparative Compound 1 in which the linker between the amine groups was biphenylrylene, and Comparative Experimental Example 2 used Comparative Compound 2 in which the structure of the curing group bonded to fluorene was different from Chemical Formula 1 of the present invention did

101: substrate
201: first electrode
301: hole injection layer
401: hole transport layer
501: light emitting layer
601: electron injection and transport layer
701: second electrode

Claims (10)

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

In Formula 1,
R1 to R11 are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. is a flag,
Ar1 and Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
n1 to n7 are each an integer of 0 to 4, n8 and n9 are each an integer of 0 to 5, n10 and n11 are each an integer of 0 to 7, and when n1 to n11 are each 2 or more, 2 or more substituents in parentheses are the same or different from each other. The method according to claim 1,
Formula 1 is a compound represented by Formula 2 below:
[Formula 2]

In Formula 2,
R1, R3 to R11, n1, n3 to n11, Ar1 and Ar2 have the same definitions as in Formula 1,
R21 and R22 are the same as or different from each other and each independently represent a substituted or unsubstituted alkyl group. The method according to claim 1,
Formula 1 is a compound represented by Formula 3 below:
[Formula 3]

In Formula 3,
Definitions of R1 to R11, n1 to n11, Ar1 and Ar2 are the same as in 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 phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group. The method according to claim 1,
The compound of Formula 1 is represented by any one of the following compounds:

. 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 provided between the first electrode and the second electrode,
At least one of the at least one 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. preparing a first electrode;
forming one or more organic material layers on the first electrode; and
Comprising the step of forming a second electrode on the at least one organic material layer,
The method of manufacturing an organic light emitting device, wherein the step of forming the at least one organic material layer comprises the step of forming the organic material layer using the coating composition of claim 6 . 10. The method of claim 9,
The step of forming an organic material layer using the coating composition is
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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