KR102364571B1 - Compound, coating compositions comprising the same, and organic light emitting device using the same - Google Patents

Abstract

The present invention relates to a compound of Formula 1, a coating composition comprising the same, and an organic light emitting device formed using the same.

Description

A compound, a coating composition comprising the same, and an organic light emitting device using the same

The present specification relates to a compound, a coating composition including the compound, and an organic light emitting device including 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 layer positioned therebetween, for example, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

As materials used in organic light emitting devices, pure organic materials or complex compounds in which organic materials and metals are complexed account for most, and depending on the use, hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. can be divided into v. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state during oxidation, is mainly used. On the other hand, as an electron injection material or an electron transport material, an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state during reduction is mainly used. As the light emitting layer material, a material having both p-type properties and n-type properties, that is, a material having a stable form in both oxidation and reduction states, is preferable. desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device additionally has the following properties.

First, it is preferable that the material used in the organic light emitting device has excellent thermal stability. This is because Joule heating occurs due to the movement of electric charges in the organic light emitting diode. Since NPB, which is currently mainly used as a material for the hole transport layer, has a glass transition temperature of 100° C. or less, it is difficult to use in an organic light emitting device that requires a high current.

Second, in order to obtain a high-efficiency organic light-emitting device capable of low voltage driving, holes or electrons injected into the organic light-emitting device should be smoothly transferred to the light emitting layer, and the injected holes and electrons should be prevented from escaping out of the light emitting layer. To this end, a material used for an organic light emitting device must have an appropriate band gap and a HOMO or LUMO energy level. In the case of PEDOT:PSS, which is currently used as a hole transport material in an organic light emitting device manufactured by a solution coating method, the LUMO energy level is lower than the LUMO energy level of an organic material used as a light emitting layer material. there are difficulties in

In addition, the material used in the organic light emitting device must have excellent chemical stability, charge mobility, and interfacial properties with an electrode or an adjacent layer. That is, the material used in the organic light emitting device should be less deformed by moisture or oxygen. In addition, it should be possible to maximize exciton formation by balancing the densities of holes and electrons in the light emitting layer of the organic light emitting device by having appropriate hole or electron mobility. In addition, for the stability of the device, it should be possible to improve the interface with the electrode including the metal or metal oxide.

Therefore, there is a demand in the art to develop an organic material having the above requirements.

Korean Patent Publication No. 2012-0112277

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

The present specification provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

L1 is Y1; X1-Y2-X2; X3-Y3-X4-Y4-X5; Y5-X6-Y6-X7-Y7; Y8-Z1-Y9; or X8-Y10-Z2-Y11-X9;

The X1 to X9 are the same as or different from each other, and each independently O, or SiR ₁₀ R ₁₁ ,

The R ₁₀ and R ₁₁ are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

wherein Y1 to Y11 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group,

Wherein Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

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

n is an integer of 0 to 2, respectively, and when n is 2, L2 are the same as or different from each other,

R1 is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted cycloalkyl group,

R2 is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

l is an integer from 0 to 8, and when l is 2 or more, R2 are the same as or different from each other,

a and b are each 1 or 2, and when a and b are 2, the linking groups in parentheses are the same as or different from each other.

In addition, the present specification provides a coating composition comprising the aforementioned compound.

In addition, the present specification is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the above-described coating composition.

The compound according to the present invention can be used as an organic material layer material of an organic light emitting device, and the compound can be processed in a solution, so that a large area of the device is possible. In particular, by using a material capable of increasing solubility and connecting the light emitting material, the light emitting layer of the organic light emitting device can be formed by a solution process, and since the molecular weight is 1000 or more, the coating property is improved in the solution process. Accordingly, fairness can be greatly improved.

The compound according to the exemplary embodiment of the present specification may be used as an organic material layer material of an organic light emitting device, and may provide characteristics of a low driving voltage and high luminous efficiency.

1 illustrates an example of an organic light emitting device according to an exemplary embodiment of the present specification.
2 is a MASS spectrum of Compound 1 according to Preparation Example 1 of the present specification.
3 is a MASS spectrum of Compound 2 according to Preparation Example 2 of the present specification.
4 is an NMR spectrum of Compound 2 according to Preparation Example 2 of the present specification.

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

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 is present between the two members.

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

Throughout this specification, the term "combination of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It is meant to include one or more selected from the group consisting of.

An exemplary embodiment of the present specification provides a compound represented by Formula 1 above.

The compound represented by Formula 1 according to an exemplary embodiment of the present invention contains a fluorene group having high photoluminescence quantum efficiency and chemical stability, and an anthracene group having excellent charge transport ability and excellent thermal stability, and is an organic compound having high efficiency and low driving voltage. A light emitting device can be manufactured. In particular, since the anthracene group included in Formula 1 has a wide band gap, it can be used as a material for an emission layer of an organic light emitting device, in particular, as a host material.

The compound represented by Formula 1 according to an exemplary embodiment of the present invention introduces a linker capable of increasing solubility between two structures consisting of anthracene and fluorene and increases the total molecular weight, thereby facilitating the solution process when preparing a thin film And there is an advantage of excellent coating properties.

As described above, by using the compound that can be used in the solution process as the organic material layer material of the organic light emitting device, the organic light emitting device can be manufactured by the solution coating method, which is economical in terms of time and cost. In addition, since the organic light emitting device can be manufactured by the solution coating method, the area of the device can be increased.

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, a position where the substituent is substitutable, is not limited, and two or more When substituted, two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" includes hydrogen; heavy hydrogen; halogen group; an alkyl group; cycloalkyl group; aryl group; and substituted or unsubstituted by one or more substituents selected from the group consisting of a heterocyclic group, or substituted or unsubstituted in which two or more substituents among the exemplified substituents are connected.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be a straight chain, branched chain, or cyclic chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- Dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2- propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, is not limited to

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto it is not

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the heterocyclic group includes at least one atom or a heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and 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 pyrimidine group, a triazine group, a triazole group, a quinolinyl group, a quinazoline group, Carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthroline group, isoxazole group, thiadiazole group, and a dibenzofuran group, but is not limited thereto.

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 heteroarylene group means that the heterocyclic group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heterocyclic group described above may be applied.

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

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is represented by any one of Formulas 2 to 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4,

Ar1, L2, R1, R2, a, b, l, n, X1 to X5 and Y1 to Y4 are the same as defined in Formula 1,

Ar2 is the same as the definition of Ar1 in Formula 1,

L3 is the same as the definition of L2 in Formula 1,

R3 is the same as the definition of R2 in Formula 1,

R4 is the same as the definition of R1 in Formula 1,

o is the same as the definition of n in Formula 1,

q is the same as the definition of l in Formula 1,

c and d are the same as defined for a in Formula 1.

In an exemplary embodiment of the present specification, L1 is Y1 or X1-Y2-X2, X1 and X2 are O, and Y1 and Y2 are the same as or different from each other, and each independently has 3 substituted or unsubstituted carbon atoms. to 20 alkylene groups.

In an exemplary embodiment of the present specification, L1 is Y1 or X1-Y2-X2, X1 and X2 are O, and Y1 and Y2 are the same as or different from each other, and each independently has 3 substituted or unsubstituted carbon atoms. to 10 alkylene groups.

In an exemplary embodiment of the present specification, L1 is Y1 or X1-Y2-X2, X1 and X2 are O, and Y1 and Y2 are alkylene groups having 3 to 10 carbon atoms.

In an exemplary embodiment of the present specification, L1 is Y1 or X1-Y2-X2, X1 and X2 are O, and Y1 and Y2 are a burentyl group, a pentylene group, or a hexylene group.

In the exemplary embodiment of the present specification, L1 is Y1 or X1-Y2-X2, X1 and X2 are O, and Y1 and Y2 are hexylene groups.

In an exemplary embodiment of the present specification, L1 is selected from the following structural formulas.

In the structural formula,

m is an integer from 3 to 12,

n1 to n2 are each an integer of 1 to 6,

R12 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

R21 is a substituted or unsubstituted cycloalkylene group; Or a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

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

In an exemplary embodiment of the present specification, R12 to R15 are the same as or different from each other, and each independently represents a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

In an exemplary embodiment of the present specification, R21 is a cyclohexylene group.

In the exemplary embodiment of the present specification, R21 is a phenylene group.

In an exemplary embodiment of the present specification, L1 is selected from the following structural formulas.

In an exemplary embodiment of the present specification, R1 is an alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 is a straight-chain alkyl group having 1 to 10 carbon atoms; a branched-chain alkyl group having 3 to 10 carbon atoms; or a cycloalkyl group having 3 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 is a straight-chain alkyl group having 1 to 10 carbon atoms; or a branched-chain alkyl group having 3 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 is a tert-butyl group or a hexyl group.

In an exemplary embodiment of the present specification, R1 is a branched-chain alkyl group having 3 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 is a tert-butyl group.

In an exemplary embodiment of the present specification, R1 is a straight-chain alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 is a hexyl group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted C6-C20 aryl group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted binaphthyl group; a substituted or unsubstituted anthracene group; a substituted or unsubstituted triphenylene group; Or a substituted or unsubstituted dibenzofuran group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted 1-naphthyl group; a substituted or unsubstituted 2-naphthyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted binaphthyl group; a substituted or unsubstituted anthracene group; a substituted or unsubstituted triphenylene group; Or a substituted or unsubstituted dibenzofuran group.

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 dibenzofuran group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with an aryl group; a naphthyl group unsubstituted or substituted with an aryl group; a biphenyl group unsubstituted or substituted with an aryl group; a binaphthyl group unsubstituted or substituted with an aryl group; an anthracene group unsubstituted or substituted with an aryl group; a triphenylene group unsubstituted or substituted with an aryl group; Or a dibenzofuran group unsubstituted or substituted with an aryl group.

In an exemplary embodiment of the specification, Ar1 is a phenyl group unsubstituted or substituted with a phenyl group or a naphthyl group; a naphthyl group unsubstituted or substituted with a phenyl group or a naphthyl group; a biphenyl group unsubstituted or substituted with a phenyl group or a naphthyl group; a binaphthyl group unsubstituted or substituted with a phenyl group or a naphthyl group; an anthracene group unsubstituted or substituted with a phenyl group or a naphthyl group; a triphenylene group unsubstituted or substituted with a phenyl group or a naphthyl group; or a dibenzofuran group unsubstituted or substituted with a phenyl group or a naphthyl group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with a phenyl group or a naphthyl group; a naphthyl group unsubstituted or substituted with a phenyl group or a naphthyl group; biphenyl group; binaphthyl group; anthracene group; triphenylene group; or a dibenzofuran group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group; naphthyl group; biphenyl group; or a dibenzofuran group.

In an exemplary embodiment of the present specification, n is 0 or 1, and L2 is an arylene group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present specification, n is 0 or 1, and L2 is a phenylene group; biphenyl group; naphthylene group; or a divalent triphenylene group .

In an exemplary embodiment of the present specification, n is 0 or 1, and L2 is a phenylene group; or a naphthylene group.

In an exemplary embodiment of the present specification, n is 0 or 1, and L2 is a phenylene group.

In an exemplary embodiment of the present specification, the molecular weight of the compound of Formula 1 is 1000 or more and 3000 or less. Preferably it is 1000 or more and 2000 or less. When the molecular weight satisfies the above range, excellent coating properties can be expected in the solution process.

In an exemplary embodiment of the present specification, the compound of Formula 1 is selected from the following structural formulas.

The compound according to an exemplary embodiment of the present application may be prepared by a manufacturing method described below.

For example, the compound represented by Formula 1 may be prepared as shown in Scheme 1 below. Substituents may be combined by methods known in the art, and the type, position or number of substituents may be changed according to techniques known in the art.

[Scheme 1]

Scheme 1 is a general reaction scheme of a compound in which L1 is X1-Y2-X2. A compound according to an exemplary embodiment of the present specification may be prepared by adjusting a substituent and a linker bonding to the phenyl group in the above reaction scheme.

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

In one embodiment of the present specification, the coating composition is for an organic light emitting device.

In one embodiment of the present specification, the coating composition includes the compound and the 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, and cyclohexanone; 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; benzoate solvents such as methyl benzoate, butyl benzoate, and 3-phenoxy benzoate; A solvent such as tetralin is exemplified, but any solvent capable of dissolving or dispersing the compound 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 another embodiment, the boiling point of the solvent is preferably 40 to 250 ℃, more preferably 60 to 230 ℃, but is not limited thereto.

In another exemplary embodiment, the viscosity of the single or mixed solvent is preferably 1 to 10 CP, more preferably 3 to 8 CP, but is not limited thereto.

In another embodiment, the concentration of the coating composition is preferably 0.1 to 20 wt/v%, more preferably 0.5 to 5 wt/v%, but is not limited thereto.

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 of the organic material layers includes a coating composition including the compound of Formula 1.

In an exemplary embodiment of the present specification, the organic material layer formed by including the coating composition is a hole transport layer, a hole injection layer, or a layer that simultaneously transports and injects holes.

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

In the exemplary embodiment of the present specification, the thickness of the light emitting layer is 50 Å to 500 Å.

In one embodiment of the present specification, the coating composition further includes a dopant, and the organic material layer including the coating composition is a light emitting layer.

In an exemplary embodiment of the present specification, the coating composition includes the compound of Formula 1 and a dopant, and Formula 1 and the dopant are included in a weight ratio of 99:1 to 50:50.

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

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, and a hole blocking layer.

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

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

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, 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 illustrates the structure of an organic light emitting device in which an anode 201, a hole injection and transport layer 301, a light emitting layer 501, an electron transport layer 601, and a cathode 701 are sequentially stacked on a substrate 101. there is.

In FIG. 1 , the light emitting layer 501 is formed using a coating composition including a compound represented by Chemical Formula 1.

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.

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 forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. 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, preparing a substrate; forming a cathode or an anode on the substrate; forming one or more organic material layers on the cathode or anode; and forming an anode or a cathode on the organic material layer, wherein at least one layer of the organic material layer is formed using the coating composition.

In one embodiment of the present specification, the organic material layer formed using the coating composition is formed using spin coating.

In another embodiment, the organic material layer formed using the coating composition is formed by 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 the organic material layer formed using the coating composition comprises: coating the coating composition on the cathode or the anode; and drying the coated coating composition.

In one embodiment of the present specification, the drying step may be performed in nitrogen, argon atmosphere or air, but is not limited thereto.

In an exemplary embodiment of the present specification, the drying may be performed through heat treatment, and the heat treatment temperature is 85°C to 250°C, preferably 100°C to 150°C.

In an exemplary embodiment of the present specification, the heat treatment time in the drying step is 1 minute to 2 hours, preferably 1 minute to 30 minutes.

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 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 metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, 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 that can transport holes from the anode or the hole injection layer to the light emitting layer and transfer them to the light emitting layer. 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 light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

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, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. In addition, a polymer compound may be used, and a polymer compound such as poly-1,4-phenylene or polyfluorene may be used, but the present invention is 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 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, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

In addition, the dopant material may include a dopant material having a maximum emission wavelength in 380 nm to 750 nm, and more preferably, a dopant having a maximum emission wavelength in 415 nm to 470 nm.

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 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, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound which prevents movement to a 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.

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 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.

In one embodiment of the present specification, the compound may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

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>

Intermediate 1a 7g (20.10mmol, 1eq), Intermediate 2a 10.38g (22.11mmol, 1.1eq), K ₂ CO ₃ 8.3g (60.06 mmol, 3eq), Pd(PPh ₃ ) ₄ (Tetrakis triphenylphosphine palladium ) 0.93 g (0.80 mmol, 0.04 eq) was placed in a 500 mL two-necked round bottom flask and charged with nitrogen. 200 mL of THF (tetrahydrofuran) and 45 mL of H ₂ O were added, and the temperature was raised to 80° C. with stirring to react overnight. After column with DCM/Hx (dichloromethane/hexane), recrystallization from EA (ethyl acetate), and precipitation in MeOH to obtain a clean intermediate A.

3g (4.33mmol, 2.2eq) of Intermediate A and 1.9g (5.83mmol, 3eq) of Cs ₂ CO ₃ in a 100 mL round-bottom flask, 30 mL of DMSO (dimethyl sulfoxide), stirred at 70° C. and activated made it 0.3 mL (1.95 mmol, 1eq) of dibromohenic acid was added dropwise and reacted overnight. The reaction was terminated with an aqueous ammonium chloride solution, washed with chloroform and water, and the organic layer was separated and water was removed with MgSO ₄ . After column with DCM/Hx and dissolved in 10 mL of dichloromethane, it was added to 150 mL of diethyl ether for precipitation. The precipitated solid was filtered to obtain 1.1 g of Compound 1.

The MASS spectrum of Compound 1 is shown in FIG. 2 .

In addition, by adjusting the naphthyl group of Intermediate 1a in Preparation Example 1 with another substituent, a compound having a different Ar1 may be prepared. Specifically, if 10-(dibenzo[b,d]furan-3-yl)anthracen-9-ylboronic acid is used instead of Intermediate 1a, a compound in which Ar1 is dibenzofuran can be prepared.

< production example 2>

Intermediate 3a 5 g (10.65 mmol, 1eq), Intermediate 4a 4.97 g (11.71 mmol, 1.1 eq), Pd(PPh ₃ ) ₄ 0.5 g (0.43 mmol, 0.04 eq), K ₂ CO ₃ 4.42 g (31.98 mmol, 3 eq) was placed in a 500 mL 2-neck round-bottom flask, vacuum dried for 10 minutes, and then filled with nitrogen. 250 mL of THF and 20 mL of H ₂ O were added and stirred while heating to 80° C. for one day. The reaction was terminated by adding water, and the organic layer was extracted by washing with EA and water. Water was removed using MgSO ₄ and charcoal (charcoal) was added to adsorb the remaining Pd (palladium) catalyst. After passing through a celite/silica/MgSO ₄ pad (celite/silica/magnesium sulfate pad), drying the solvent, purification through an EA/Hx column, and washing with EA to obtain an intermediate B.

Intermediate B 3g (3.90mmol, 2.0eq) was dissolved in 40mL of DMSO, Cs ₂ CO ₃ 2g (6.14mmol, 3.1eq) was added, and stirred at 55° C. for 30 minutes while heating. Dibromohexane 0.3mL (1.95mmol, 1eq) was injected (injection) and reacted at 55 ℃ overnight. After washing with chloroform/water to extract the organic layer, water was dried over MgSO ₄ . After that, it was passed through a celite/silica/MgSO ₄ pad, dried, and then columned with DCM/Hx. The solvent was dried in vacuo, and the obtained material was dissolved in 10 mL of dichloromethane, added to 150 mL of diethyl ether, and filtered to obtain Compound 2.

The MASS spectrum of Compound 2 is shown in FIG. 3 .

The NMR spectrum of Compound 2 is shown in FIG. 4 .

< production example 3>

In Preparation Example 2, Compound 3 was prepared in the same manner as in Preparation Example 2, except that 2-bromoethyl ether was used instead of dibromohexane.

In addition, various compounds satisfying L1 of the present invention may be prepared by adjusting the substituents such as 3a and dibromohexane of Preparation Example 2, or by a similar method.

< Example >

Example One

compound A compound B

compound C

A glass substrate coated with indium tin oxide (ITO) to a thickness of 500 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. Ultrasonic cleaning with acetone, distilled water, isopropyl alcohol solvent and drying.

AI4083 (PEDOT:PSS) was spin-coated on the prepared ITO transparent electrode to form a hole injection layer with a thickness of 400 Å, and then heat-treated on a hot plate at 120° C. for 15 minutes.

On the hole injection layer, a composition obtained by dissolving the compound A in an organic solvent (toluene) at a weight ratio of 1% was spin-coated to form a hole transport layer having a thickness of 200 Å, and under N ₂ atmosphere, on a hot plate at 200 ° C., for 30 minutes. The coating composition was cured.

On the hole transport layer, a composition obtained by dissolving Compound 1 and Compound B prepared in Preparation Example 1 in a ratio of 94:6 in toluene at a weight ratio of 0.5% was spin-coated to form a light emitting layer having a thickness of 200 Å, and a hot plate under N ₂ atmosphere. The coating composition was dried at 120 °C for 10 minutes.

Thereafter, the device was manufactured by sequentially depositing the compound C (350 Å), LiF (10 Å), and Al (1000 Å) in a vacuum evaporator. In the above process, the deposition rate of compound C, which is the material of the electron transport layer, was maintained at 1 to 2 Å/sec, the deposition rate of LiF of the cathode was 0.1 Å/sec, and the deposition rate of aluminum (Al) was maintained at 2 Å/sec, During deposition, the vacuum was maintained at 2×10 ^-7 to 5×10 ^-8 torr.

Example 2

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 2 prepared in Preparation Example 2 was used instead of Compound 1 in Example 1.

Example 3

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 3 prepared in Preparation Example 3 was used instead of Compound 1 in Example 1.

comparative example One

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the following comparative compound was used instead of Compound 1 in Example 1.

[Comparative compound]

The results of measuring the driving voltage, current efficiency, and lifespan of the organic light emitting diodes prepared in Examples 1 to 3 and Comparative Example 1 are shown in Table 1 below.

light-emitting compound drive voltage
(V) current efficiency
(cd/A) Power efficiency (lm/W) T50(hr) at 20mA/cm ² Example 1 compound 1 compound B 5.01 3.73 2.34 28 Example 2 compound 2 compound B 4.94 3.57 2.26 25 Example 3 compound 3 compound B 4.97 3.66 2.31 26 Comparative Example 1 comparative compound compound B 5.09 2.98 1.84 21

From Table 1, it can be confirmed that Examples 1 to 3 using the compound of the present specification are superior to Comparative Example 1 in efficiency and lifespan characteristics.

101: substrate
201: anode
301: hole injection and transport layer
501: light emitting layer
601: electron transport layer
701: cathode

Claims (12)

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

In Formula 1,
Ar1 is an unsubstituted aryl group,
L1 is X1-Y2-X2; or X3-Y3-X4-Y4-X5;
Wherein X1 to X5 are O,
wherein Y2 to Y4 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group,
L2 is a direct bond; phenylene group; or a naphthylene group,
n is 0 or 1,
R1 is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted cycloalkyl group,
R2 is hydrogen,
l is an integer from 0 to 8,
a and b are 1. The method according to claim 1, wherein the compound represented by Formula 1 is a compound represented by any one of the following Formulas 3 to 4:
[Formula 3]

[Formula 4]

In Formulas 3 to 4,
Ar1, L2, R1, R2, a, b, l, n, X1 to X5 and Y2 to Y4 are the same as defined in Formula 1,
Ar2 is the same as the definition of Ar1 in Formula 1,
L3 is the same as the definition of L2 in Formula 1,
R3 is the same as the definition of R2 in Formula 1,
R4 is the same as the definition of R1 in Formula 1,
o is the same as the definition of n in Formula 1,
q is the same as the definition of l in Formula 1,
c and d are the same as defined for a in Formula 1. The compound of claim 1, wherein L1 is selected from the following structural formulas:

In the structural formula,
m is an integer from 3 to 12,
n1 is an integer from 1 to 6. The compound according to claim 1, wherein R1 is a tert-butyl group or a hexyl group. The method according to claim 1, wherein Ar1 is an unsubstituted phenyl group; or an unsubstituted naphthyl group. delete The compound according to claim 1, wherein the molecular weight of the compound of Formula 1 is 1000 or more and 3000 or less. The compound of claim 1, wherein the compound of Formula 1 is selected from the following structural formulas:

A coating composition comprising a compound according to any one of claims 1 to 5, 7 and 8. 10. The method of claim 9,
The coating composition is a coating composition for an organic light emitting device. a first electrode; a second electrode provided to face the first electrode; and
At least one organic material layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising the coating composition of claim 9. The organic light emitting device of claim 11 , wherein the organic material layer including the coating composition is a light emitting layer.

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