KR20190096139A - Compound, coating composition comprising the same, organic light emitting device using the same and method of manufacturing the same - Google Patents

Abstract

The present specification relates to: a compound represented by chemical formula 1; a coating composition comprising the compound; an organic light emitting device formed by using the coating composition; and a method for manufacturing the same. The compound according to an embodiment of the present specification can be used as a material of an organic material layer of the organic light emitting device, and thus can lower driving voltage of the organic light emitting device.

Description

Compound, coating composition comprising same, organic light emitting device using same and manufacturing method thereof {COMPOUND, COATING COMPOSITION COMPRISING THE SAME, ORGANIC LIGHT EMITTING DEVICE USING THE SAME AND METHOD OF MANUFACTURING THE SAME}

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

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

Conventionally, a deposition process has been mainly used to manufacture an organic light emitting device. However, there is a problem in that a lot of material loss occurs when manufacturing the organic light emitting device by the deposition process, in order to solve this problem, a technique for manufacturing a device through a solution process that can increase the production efficiency due to low material loss There is a need for development of materials that can be used in solution processing.

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

First, it should be possible to form a homogeneous solution that can be stored. Commercially available deposition process materials have good crystallinity, so they do not dissolve well in the solution or crystals are easily formed even when the solution is formed. Therefore, the concentration gradient of the solution may vary depending on the storage period, or a defective device may be formed.

Second, the material used in the solution process should be excellent in coating properties to form a thin film of uniform thickness without the formation of holes or agglomeration phenomenon, and excellent current efficiency in manufacturing an organic light emitting device, Good lifespan characteristics are required.

Korean Unexamined Patent Publication No. 10-2004-0028954

The present specification is to provide a compound, a coating composition comprising the compound, an organic light emitting device formed using the coating composition and a method of manufacturing the same.

The present specification provides a compound represented by the following Formula 1.

[Formula 1]

In Chemical Formula 1,

L1 to L6 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

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

R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxyl group; Nitrile group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

r1 to r4 are each an integer of 1 or 2,

When r1 to r4 are each 2, R1 to R4 of 2 are the same as or different from each other,

r5 to r7 and r10 to r12 are each an integer of 1 to 4,

r8 and r9 are each an integer of 1 to 3,

When r5 to r12 are each 2 or more, two or more R5 to R12 are the same as or different from each other.

In addition, the present disclosure provides a coating composition comprising the 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 coating composition.

In addition, the present specification is a step of preparing a substrate; Forming a first electrode on the substrate; Forming at least one organic material layer on the first electrode; And forming a second electrode on the organic material layer, wherein forming the organic material layer includes forming at least one organic material layer using the coating composition. do.

The compound according to the exemplary embodiment of the present specification may be a solution process, so that a large area of the device may be possible and may be used as a material of the organic material layer of the organic light emitting device.

In addition, the compound according to the exemplary embodiment of the present specification can be used as a material of the organic material layer of the organic light emitting device, it is possible to lower the driving voltage of the organic light emitting device.

In addition, the compound according to an exemplary embodiment of the present specification can be used as a material of the organic material layer of the organic light emitting device, it is possible to improve the light efficiency.

In addition, the compound according to an exemplary embodiment of the present specification can be used as a material of the organic material layer of the organic light emitting device, it is possible to improve the life characteristics of the device by the thermal stability of the compound.

In addition, the compound according to an exemplary embodiment of the present specification can be used as a material of the organic material layer of the organic light emitting device, there is an advantage that does not change the color coordinates without inhibiting solubility.

1 illustrates an example of an organic light emitting diode according to an exemplary embodiment of the present specification.

Hereinafter, this specification is demonstrated in detail.

The present specification provides a compound represented by the following Formula 1.

When used in an organic light emitting device, pyrene has an excellent effect as a high luminance light emitter, but has a disadvantage of poor solubility. Compound represented by the formula (1) of the present specification can effectively lower the y value of the color coordinates by including a dibenzofuran group in the core structure of pyrene. In addition, the compound represented by the formula (1) of the present specification includes a fluorenyl group, there is an advantage that can introduce a variety of substituents, without affecting the luminescence properties of the pyrene core structure. Therefore, the compound represented by the formula (1) of the present specification has an advantage of ensuring the solubility of the pyrene derivative sufficiently while not changing the color coordinates of the substituent.

As used herein, the term "solubility" refers to a property in which a solute is soluble in a specific solvent, and may be expressed as the number of g of a solute that can be dissolved in 100 g of a solvent at a constant temperature.

In this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.

In the present specification, when a part "contains" a certain component, this means that the component may further include other components, except for the case where there is no contrary description.

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

는 연결되는 부위를 의미한다.In the present specification,

Means a site to be connected.

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

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Hydroxyl group; Alkyl groups; Cycloalkyl group; Silyl groups; Aryl group; And one or two or more substituents selected from the group consisting of a heterocyclic group including one or more of N, O, S, Se, and Si atoms, or two or more substituents among the substituents exemplified above are substituted with a substituent, or any It means that it does not have a substituent.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms. 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, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and more preferably 3 to 30 carbon atoms. 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, and the like, but is not limited thereto.

In the present specification, the silyl group is a substituent including Si and the Si atom is directly connected as a radical, represented by -SiR ₂₀₁ R ₂₀₂ R ₂₀₃ , and R ₂₀₁ to R ₂₀₃ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; An alkyl group; Alkenyl groups; An alkoxy group; Cycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. It is not limited.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group.

In the present specification, when the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 50 carbon atoms, more preferably 6 to 30 carbon atoms. Specifically, monocyclic aryl groups include, but are not limited to, phenyl groups, biphenyl groups, terphenyl groups, quarterphenyl groups, and the like.

In the present specification, when the aryl group is a polycyclic aryl group, carbon number is not particularly limited. It is preferable that it is C10-50, and it is more preferable that it is C10-30. Specifically, the polycyclic aryl group includes, but is not limited to, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

Etc., but is not limited thereto.

In the present specification, the heterocyclic group includes one or more of N, O, S, Si, and Se as heteroatoms, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms, and more preferably 2 to 30 carbon atoms. desirable. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acri Din group, pyridazine group, pyrazine group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carba Drowsiness, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthroline group, phentrithrol group (pteridine), thiazolyl Group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, dibenzofuran group, and the like, but is not limited thereto.

In the present specification, the heteroaryl group may be selected from examples of the heterocyclic group except that the heteroaryl group is aromatic, but is not limited thereto.

In the present specification, the arylene group refers to a divalent group having two bonding positions in the aryl group. The description of the aforementioned aryl group can be applied except that they are each divalent.

In the present specification, the heteroarylene group means a divalent group having two bonding positions in the heteroaryl group. The description of the aforementioned heteroaryl group can be applied except that they are each divalent.

In one embodiment of the present specification, L1 to L6 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

In one embodiment of the present specification, L1 and L3 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L1 and L3 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, or a substitution Or an unsubstituted fluorenylene group.

In one embodiment of the present specification, L1 is a phenylene group.

In one embodiment of the present specification, L1 is a biphenylene group.

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

In one embodiment of the present specification, L3 is a biphenylene group.

In one embodiment of the present specification, L2 and L4 are each a direct bond.

In one embodiment of the present specification, L5 and L6 are each a direct bond.

In one embodiment of the present specification, L5 and L6 are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L5 and L6 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, or a substitution Or an unsubstituted fluorenylene group.

In one embodiment of the present specification, L5 and L6 are each a phenylene group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

In one 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 alkyl group having 1 to 20 carbon atoms.

In one 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 alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl Group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted isopropyl group, or a substituted or unsubstituted tert-butyl group.

In one embodiment of the present specification, Ar1 and Ar2 are each hexyl group.

In one 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 aryl group having 6 to 50 carbon atoms.

In one 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 aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted group Fluorenyl group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently a phenyl group unsubstituted or substituted with an alkyl group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently substituted or unsubstituted with a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, or tert-butyl group It is a phenyl group.

In one embodiment of the present specification, Ar1 and Ar2 are each a phenyl group substituted with a hexyl group.

In one embodiment of the present specification, Ar1 and Ar2 are each a phenyl group substituted with a tert-butyl group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently substituted or unsubstituted with a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, or tert-butyl group It is a ring biphenyl group.

In one embodiment of the present specification, Ar1 and Ar2 are each a biphenyl group substituted with a hexyl group.

In one embodiment of the present specification, Ar1 and Ar2 are each a biphenyl group substituted with a tert-butyl group.

In one embodiment of the present specification, R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxyl group; Nitrile group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, r1 to r4 are each an integer of 1 or 2, when r1 to r4 are each 2, R1 to R4 of 2 are the same as or different from each other, r5 to r7 and r10 to r12 is an integer of 1 to 4, respectively, r8 and r9 are each an integer of 1 to 3, and when r5 to r12 are each 2 or more, two or more R5 to R12 are the same as or different from each other.

In one embodiment of the present specification, R1 to R12 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R1 to R12 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl Group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted isopropyl group, or a substituted or unsubstituted tert-butyl group.

In one embodiment of the present specification, R1 and R3 are each isopropyl group.

In one embodiment of the present specification, R2 and R4 to R12 are each hydrogen.

In one embodiment of the present specification, R1 to R12 are each hydrogen.

In one embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formula 2 or 3.

[Formula 2]

[Formula 3]

In Chemical Formula 2 or 3,

Definitions for L1 to L6, Ar1, Ar2, R1 to R12 and r1 to r12 are the same as defined in Chemical Formula 1.

In one embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 4 to 11.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Chemical Formulas 4 to 11,

The definitions for L1 to L6, Ar1, Ar2, R1 to R12 and r1 to r12 are the same as those defined in Chemical Formula 1.

In one embodiment of the present specification, the compound represented by Formula 1 is any one selected from the following compounds.

The present specification provides a coating composition comprising the compound.

According to an exemplary embodiment of the present specification, the coating composition may further include a solvent.

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

In one embodiment of the present specification, the solvent is, for example, a chlorine 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; Polyhydric compounds 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; Amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; Benzoate solvents such as methyl benzoate, butyl benzoate and 3-phenoxy benzoate; And a solvent such as tetralin, but may be used as long as it is a solvent capable of dissolving or dispersing the compound according to one embodiment of the present specification, and the like.

In another exemplary embodiment, the solvent may be used alone or in combination of two or more solvents.

In another exemplary embodiment, the boiling point of the solvent is preferably 40 ° C to 250 ° C, more preferably 60 ° C to 230 ° C, but is not limited thereto.

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

In another embodiment, the concentration of the coating composition is preferably 0.1 wt / v% to 20 wt / v%, more preferably 0.5 wt / v% 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; 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 the coating composition.

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

In another embodiment, the first electrode is an anode, and the second electrode is a cathode.

In one embodiment of the present specification, the organic material layer including the coating composition is a hole transport layer, a hole injection layer or a layer for simultaneously transporting holes and hole injection.

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

In another exemplary embodiment, the organic material layer including the coating composition is a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1 as a host of the light emitting layer.

According to another exemplary embodiment, the organic material layer including the coating composition is a light emitting layer, and the light emitting layer includes the compound represented by Chemical Formula 1 as a host of the light emitting layer, and may further include a dopant material. At this time, the mass ratio of the host and the dopant (host: dopant) is 80:20 to 99: 1. Specifically, it may be 90:10 to 99: 1, and more specifically 90:10 to 95: 5.

In another exemplary embodiment, the organic material layer including the coating composition is a light emitting layer, and the light emitting layer includes the compound represented by Chemical Formula 1 as a dopant of the light emitting layer.

In another exemplary embodiment, the organic material layer may include a layer for simultaneously injecting holes and transporting holes and a light emitting layer, and the light emitting layer may further include a dopant material.

The dopant materials may be those known in the art, for example, but are not limited to Paren or Chrysene series materials.

In one embodiment of the present specification, the organic light emitting device is a hole injection layer, a hole transport layer. It may further comprise one or two 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 another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure in which an anode, at least one organic material layer, and a cathode are sequentially stacked on a substrate.

In another exemplary embodiment, the organic light emitting device may be an organic light emitting device having an inverted type 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 be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present specification 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 and the like 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 the exemplary embodiment of the present specification is illustrated in FIG. 1.

1 illustrates an organic light emitting diode in which an anode 201, a hole injection layer 301, a hole transport layer 401, an emission layer 501, an electron transport layer 601, and a cathode 701 are sequentially stacked on a substrate 101. The structure of the device is illustrated.

In one embodiment of the present specification, the hole injection layer 301, the hole transport layer 401 or the light emitting layer 501 of FIG. 1 may be formed using a coating composition containing a compound represented by the formula (1).

In one embodiment of the present specification, the hole injection layer 301 of FIG. 1 may be formed using a coating composition including the compound represented by Chemical Formula 1.

In one embodiment of the present specification, the hole transport layer 401 of FIG. 1 may be formed using a coating composition including the compound represented by Chemical Formula 1.

In one embodiment of the present specification, the emission layer 501 of FIG. 1 may be formed using a coating composition including the compound represented by Chemical Formula 1.

1 illustrates an organic light emitting diode and 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 represented by Chemical Formula 1.

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 physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. Form. An organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer may be formed on the substrate through a deposition or a solution process, and then deposited thereon, which may be used as a cathode. In addition to such a 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.

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of anode materials that can be used herein include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; And conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole, polyaniline, and the like, but are not limited thereto. .

The cathode material is generally a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the cathode materials include metals such as barium, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; And multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and a material having a hole injection effect at the anode, and an excellent hole injection effect to the light emitting layer or the light emitting material is preferred as the hole injection material. In addition, a compound which prevents movement of the excitons generated in the light emitting layer to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable. In addition, 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 may include metal porphyrin, oligothiophene, and arylamine-based organic material; Hexanitrile hexaazatriphenylene-based organic material; Quinacridone series organics; Perylene-based organic material; And 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 holes to the light emitting layer. The hole transport material is a material capable of transporting holes from an anode or a hole injection layer and transferring them to the light emitting layer. The 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 region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. Examples of the host material include a condensed aromatic ring derivative or a hetero ring-containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladders. Type furan compounds, pyrimidine derivatives, and the like, but is not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, pyrene derivatives, metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, and includes pyrene, anthracene, chrysene, periplanthene and the like having an arylamine group. In addition, the styrylamine compound is a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine, and the substituted or unsubstituted arylamine is an aryl group, silyl group, alkyl group, cycloalkyl group and arylamine group. In the group consisting of one or two or more substituents selected means a substituted or unsubstituted arylamine group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron injection layer is a layer for injecting electrons from the electrode, it is preferable to have the ability to transport electrons to the electron injection material, and to have an excellent electron injection effect from the cathode, the light emitting layer or the light emitting material. In addition, a compound which prevents movement of the excitons generated in the light emitting layer to the hole injection layer and has excellent thin film forming ability is preferable. Specific examples include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, benzoimidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone. And derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer. The electron transporting material is a material that can inject electrons well from the cathode and transfer the electrons to the light emitting layer. Suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; And hydroxyflavone-metal complexes, and the like, but are not limited thereto. In addition, the electron transport layer can be used with any desired cathode material, as used in accordance with the prior art. In particular, suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specific examples are cesium, barium, calcium, ytterbium and samarium, each followed by an aluminum or silver layer.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper and bis (8-hydroxyquinolinato) Manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [ h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato ) (o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) 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 for preventing the cathode from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specific examples include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a 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.

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 first electrode on the substrate; Forming at least one organic material layer on the first electrode; And forming a second electrode on the organic material layer, wherein forming the organic material layer includes forming at least one organic material layer using the coating composition.

In one embodiment of the present specification, the step of forming at least one organic layer using the coating composition uses a spin coating method.

In another embodiment, the step of forming at least one organic layer using the coating composition uses a printing method.

In the state of 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.

The coating composition according to an exemplary embodiment of the present specification has an economical effect in time and cost at the time of manufacturing the device because it can be formed by a printing method to suit the solution process as a structural characteristic.

In one embodiment of the present specification, the step of forming one or more organic material layers using the coating composition comprises the steps of coating the coating composition on the first electrode; And drying the coated coating composition.

In one embodiment of the present specification, the drying may be performed by heat treatment, and the heat treatment temperature in the drying by heat treatment may be 60 ° C. to 180 ° C., and according to one embodiment, may be 80 ° C. to 180 ° C. And in another embodiment, it may be 120 ℃ to 180 ℃.

In another embodiment, the heat treatment time in the step of drying by heat treatment is 1 minute to 1 hour, according to one embodiment may be 1 minute to 30 minutes, in another embodiment, 10 minutes To 30 minutes. When the range of the heat treatment time is satisfied, the solvent may be completely removed.

When the step of drying by heat treatment in the step of forming at least one organic layer using the coating composition, when the other layer is laminated on the surface of the organic layer formed by using the coating composition, is dissolved by a solvent, It can be morphologically affected or prevent degradation.

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

< Production Example >

< Production Example  1>

(1) Synthesis of Intermediate 1

Intermediate 1-1 (2 g, 2.75 mmol), Intermediate 1-2 (603 mg, 3.3 mmol) and NaOtBu (tert-butoxysodium) (396 mg, 4.12 mmol) were placed in a 250 ml round bottom flask. 100 ml of Toluene was added under nitrogen and the temperature was raised to 100 ° C. Pd (P (tBu ₃ )) ₂ (70mg, 0.14mmol) was placed in a round bottom flask and the light was blocked and stirred for 8 hours. After lowering the temperature, the material was extracted using DCM (Dichloromethane) and water, and stirred with MgSO ₄ and acid clay. After passing through silica gel, the solvent was removed. The material was separated by column chromatography (methyl chloride / Hexane).

(2) Synthesis of Compound BD10

The intermediate 1 (2 g, 3.27 mmol), intermediate P (726 mg, 1.63 mmol), and NaOtBu (471 mg, 4.9 mmol) were placed in a 250 ml round bottom flask. 100 ml of Toluene was added under nitrogen and the temperature was raised to 100 ° C. Pd (P (tBu ₃ )) ₂ (84 mg, 0.16 mmol) was placed in a round bottom flask and the light was blocked and stirred for 2 hours. After lowering the temperature, the material was extracted using DCM (Dichloromethane) and water, and stirred with MgSO ₄ and acid clay. After passing through silica gel, the solvent was removed. Compound BD10 was obtained by separating the material through column chromatography (methyl chloride / Hexane).

Compound BD10

¹ H-NMR (CDCl ₃ ): 8-7.85 (6H), 7.68 (4H), 7.62 (4H), 7.54-7.5 (6H), 7.37-7.26 (14H), 7.25 (2H), 7.15 (4H), 7.02 (4H), 6.97-6.83 (4H), 2.88 (2H), 1.31 (48H)

< Production Example  2>

(1) Synthesis of Intermediate 2

250 mL round bottom of intermediate 1-1 (3 g, 4.12 mmol), intermediate 2-1 (620 mg, 4.53 mol), Pd (PPh ₃ ) ₄ (238 mg, 0.21 mmol), K ₂ CO ₃ (1.7 g, 12.4 mmol) Put it in a flask. 100 ml of THF (Tetrahydrofuran) and 25 ml of H ₂ O were added under nitrogen, and the temperature was raised to 80 ° C. and stirred for 8 hours. After lowering the temperature and extracting the material using DCM (Dichloromethane) and water, MgSO ₄ and acid clay were added and stirred. After passing through silica gel, the solvent was removed. The material was separated by column chromatography (methyl chloride / Hexane).

(2) Synthesis of Intermediate 3

Intermediate 2 (2.53 g, 4.85 mmol), Intermediate 3-1 (1 g, 4.05 mmol), and NaOtBu (584 mg, 6.07 mmol) were placed in a 250 ml round bottom flask. 100 ml of Toluene was added under nitrogen and the temperature was raised to 100 ° C. Pd (P (tBu ₃ )) ₂ (103mg, 0.2mmol) was put into a round bottom flask and the light was blocked and stirred for 2 hours. After lowering the temperature and extracting the material using DCM (Dichloromethane) and water, MgSO ₄ and acid clay were added and stirred. After passing through silica gel, the solvent was removed. The material was separated by column chromatography (methyl chloride / Hexane).

(3) Synthesis of Compound BD14

Intermediate 3 (2 g, 2.9 mmol), Intermediate P (645.7 mg, 1.45 mmol), and NaOtBu (419 mg, 4.36 mmol) were placed in a 250 ml round bottom flask. 100 ml of Toluene was added under nitrogen and the temperature was raised to 100 ° C. Pd (P (tBu ₃ )) ₂ (74mg, 0.14mmol) was placed in a round bottom flask and the light was blocked and stirred for 2 hours. After lowering the temperature and extracting the material using DCM (Dichloromethane) and water, MgSO ₄ and acid clay were added and stirred. After passing through silica gel, the solvent was removed. Compound BD14 was obtained by separating the material by column chromatography (methyl chloride / Hexane).

Compound BD14

¹ H-NMR (CDCl ₃ ): 8.08-7.9 (8H), 7.69-7.62 (8H), 7.52 (6H), 7.4-7.28 (28H), 7.12 (2H), 7.02 (4H), 6.96 (2H), 2.88 (2H), 1.31 (48H)

< Production Example  3>

Intermediate 1 (2 g, 3.27 mmol), Intermediate PP (828.7 mg, 1.63 mmol), and NaOtBu (471 mg, 4.9 mmol) were placed in a 250 ml round bottom flask. 100 ml of Toluene was added under nitrogen and the temperature was raised to 100 ° C. Pd (P (tBu ₃ )) ₂ (83.5mg, 0.16mmol) was put in a round bottom flask and the light was blocked and stirred for 2 hours. After lowering the temperature and extracting the material using DCM (Dichloromethane) and water, MgSO ₄ and acid clay were added and stirred. After passing through silica gel, the solvent was removed. Compound BD26 was obtained by separating the material by column chromatography (methyl chloride / Hexane).

Compound BD26

¹ H-NMR (CDCl ₃ ): 8.2-7.9 (8H), 7.69-7.65 (6H), 7.54 (10H), 7.38-7.27 (20H), 7.17 (4H), 7.02-6.85 (10H), 2.89 (2H ), 1.32 (48 H)

< Production Example  4>

Intermediate 3 (2 g, 2.9 mmol), Intermediate PP (507 mg, 1.45 mmol), and NaOtBu (419 mg, 4.36 mmol) were placed in a 250 ml round bottom flask. 100 ml of Toluene was added under nitrogen and the temperature was raised to 100 ° C. Pd (P (tBu ₃ )) ₂ (74mg, 0.14mmol) was placed in a round bottom flask and the light was blocked and stirred for 2 hours. After lowering the temperature and extracting the material using DCM (Dichloromethane) and water, MgSO ₄ and acid clay were added and stirred. After passing through silica gel, the solvent was removed. Compound BD30 was obtained by separating the material by column chromatography (methyl chloride / Hexane).

Compound BD30

¹ H-NMR (CDCl ₃ ): 8.2-7.9 (10H), 7.7 (4H), 7.62 (2H), 7.54 (10H), 7.39-7.28 (32H), 7.14 (2H), 7.02-6.97 (6H), 2.86 (2H), 1.29 (48H)

< Example >

< Example  1>

[Compound IB] [Compound A]

[Compound B]                [Compound C]

[Compound D] [Compound E]

The P doping material (Compound IB), Compound A, and an organic solvent (cyclohexanone) were mixed to prepare a coating composition. The ratio of Compound A and p-dopant (Compound IB) (Compound A: p-dopant) was mixed at a weight ratio of 8: 2. ITO (indium tin oxide) was deposited in a thin film deposited glass substrate in a thickness of 1,500Å in a detergent-dissolved distilled water and washed for 30 minutes by ultrasonic. Thereafter, the ultrasonic cleaning was performed twice with distilled water for 10 minutes. After the distilled water was washed, the ultrasonic washing with a solvent of isopropyl alcohol and acetone for 30 minutes each and dried, and then transported the substrate to the glove box.

The coating composition was spin-coated on the prepared ITO transparent electrode to form a hole injection layer having a thickness of 300 μm, and the coating composition was cured at 220 ° C. and 30 minutes in a hot plate under a nitrogen atmosphere. On the hole injection layer, a composition in which Compound A was dissolved in an organic solvent (toluene) at a weight ratio of 1% was spin coated to form a hole transport layer having a thickness of 400 mm 3. Thereafter, the coating composition was cured at 230 ° C. and 30 minutes in a hot plate under a nitrogen atmosphere. On the hole transport layer, spin-coating a composition obtained by dissolving Compound B and Compound BD10 (8% concentration) in an organic solvent (toluene) at a weight ratio of 0.6% to form a light emitting layer having a thickness of 200 μs, and a hot plate under a nitrogen atmosphere. The coating composition was cured at 120 ° C. and 10 min conditions.

Subsequently, the compound E was transferred to a vacuum evaporator (thickness: 200 kPa), LiF (thickness: 12 kPa), and aluminum (Al) (thickness: 2,000 kPa) were sequentially deposited to manufacture an organic light emitting device. Was the deposition rate of the organic material in the above process, maintaining the range of 0.4 to 0.7Å / sec, LiF of the cathode was 0.3 Å / sec, the aluminum is 2 Å / sec was maintained at a deposition rate of, During the deposition, a vacuum 2 X 10 ^-7 To 5 × 10 ⁻⁸ torr.

< Example  2>

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound BD14 instead of the compound BD10 in Example 1.

< Example  3>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound BD26 was used instead of Compound BD10 in Example 1.

< Example  4>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound BD30 was used instead of Compound BD10 in Example 1.

< Comparative example  1>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound C was used instead of Compound BD10 in Example 1.

< Comparative example  2>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound D was used instead of Compound BD10 in Example 1.

Table 1 shows the results of measuring the driving voltage and the efficiency of the organic light emitting diodes manufactured by Examples 1 to 4, Comparative Example 1, and Comparative Example 2 at a current density of 10 mA / cm ² .

Further, Compound BD10, Compound BD14, Compound BD26, Compound BD30, Compound C, and Compound D used in Examples 1 to 4, Comparative Example 1, and Comparative Example 2 were added to a solvent (100 ml of toluene), respectively, and then stored at room temperature ( 25 ° C.) for 30 minutes. Thereafter, the laser was passed through the solution to determine whether a precipitate occurred through the tindall effect, and the amount of dissolution was measured. By repeating the above process, the results are shown in Table 1 below.

division Dopant Solubility
(wt%) Driving voltage
(V) Emission wavelength (nm) Current Efficiency (cd / A) Power efficiency
(lm / W) Example 1 Compound bd10 1.5 5.43 455 4.15 2.13 Example 2 Compound bd14 1.3 5.50 460 4.46 2.46 Example 3 Compound bd26 1.2 5.54 450 4.24 2.25 Example 4 Compound bd30 1.0 5.40 453 4.56 2.68 Comparative Example 1 Compound C 0.1 6.23 465 3.09 1.45 Comparative Example 2 Compound D 0.8 5.82 472 3.75 1.84

As shown in Table 1, the organic light emitting device of Examples 1 to 4 using the compound represented by the formula (1) of the present specification shows the characteristics of low voltage and high efficiency, compared to Comparative Example 1 and Comparative Example 2, It was confirmed that it can be applied to the light emitting device.

Specifically, when the compound represented by Formula 1 of the present specification is used as the dopant of the light emitting layer, it can be seen that the solubility is improved and the emission wavelength is closer to deep blue compared to Comparative Example 1 and Comparative Example 2. In addition, due to such improved solubility, when the device performance is evaluated by the solution process, it can be seen that the driving voltage is lowered, the power efficiency is increased. Particularly, in Comparative Example 2, since the substitution positions of Formula 1 and the fluorene group of the present specification are different, the light emission wavelength appeared in the long wavelength region, and thus, it was found that the light emission device was not suitable for the blue light emitting device.

Although the preferred embodiments of the present specification have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention. Belong.

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

Claims (11)

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

In Chemical Formula 1,
L1 to L6 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Hydroxyl group; Nitrile group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
r1 to r4 are each an integer of 1 or 2,
When r1 to r4 are each 2, R1 to R4 of 2 are the same as or different from each other,
r5 to r7 and r10 to r12 are each an integer of 1 to 4,
r8 and r9 are each an integer of 1 to 3,
When r5 to r12 are each 2 or more, two or more R5 to R12 are the same as or different from each other. The compound of claim 1, wherein Formula 1 is represented by Formula 2 or 3:
[Formula 2]

[Formula 3]

In Chemical Formula 2 or 3,
Definitions for L1 to L6, Ar1, Ar2, R1 to R12 and r1 to r12 are the same as defined in Chemical Formula 1. The compound of claim 1, wherein Formula 1 is represented by one of Formulas 4 to 11:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Chemical Formulas 4 to 11,
The definitions for L1 to L6, Ar1, Ar2, R1 to R12 and r1 to r12 are the same as those defined in Chemical Formula 1. The compound of claim 1, wherein the compound represented by Chemical Formula 1 is any one selected from the following compounds:

Coating composition comprising a compound according to any one of claims 1 to 4. 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 5. The method according to claim 6, wherein the organic layer including the coating composition is a hole transport layer, a hole injection layer or a layer for simultaneously transporting holes and hole injection, the hole transport layer, a hole injection layer or a layer for both hole transport and hole injection at the same time is the An organic light emitting device comprising the coating composition. The organic light emitting device of claim 6, wherein the organic material layer including the coating composition comprises a light emitting layer, and the light emitting layer comprises the coating composition. Preparing a substrate;
Forming a first electrode on the substrate;
Forming at least one organic material layer on the first electrode; And
Forming a second electrode on the organic material layer;
Forming the organic layer comprises the step of forming at least one organic layer using the coating composition of claim 5 organic light emitting device manufacturing method. The method of claim 9, wherein the forming of the at least one organic material layer using the coating composition uses an inkjet coating method or a spin coating method. The method of claim 9, wherein forming at least one organic layer using the coating composition comprises: coating the coating composition on the first electrode; And
Method of manufacturing an organic light emitting device comprising the step of drying the coated coating composition.

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