KR102105741B1 - Fluorene derivatives, coating composition comprising fluorene derivatives, organic light emitting diode using the same and method of manufacturing the same - Google Patents

Abstract

The present specification relates to a fluorene derivative, a coating composition containing the fluorene derivative, an organic light emitting device using the same, and a method for manufacturing the same.

Description

Fluorene derivatives, coating compositions containing fluorene derivatives, organic light-emitting device using the same, and manufacturing method thereof

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

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

As a material used in the organic light emitting device, a pure organic material or a complex compound in which an organic material and a metal are complex occupies most, and depending on the purpose, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. It can be divided into. Here, as a hole injection material or a 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. The light emitting layer material is preferably a material having both p-type and n-type properties, that is, a material having a stable form in both the oxidation and reduction states, and a material having high luminous efficiency that converts it to light when excitons are formed. desirable.

In addition to the above-mentioned, 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 is caused by the movement of electric charges in the organic light emitting device. Currently, NPB, which is mainly used as a hole transport layer material, has a glass transition temperature of 100 ° C. or less, and thus is difficult to use in an organic light emitting device requiring high current.

Secondly, in order to obtain a high-efficiency organic light-emitting device capable of driving a low voltage, holes or electrons injected into the organic light-emitting device must be smoothly transferred to the light-emitting layer, and at the same time, injected holes and electrons must be prevented from exiting the light-emitting layer. To this end, the material used in the organic light emitting device should have an appropriate band gap and HOMO or LUMO energy level. In the case of PEDOT: PSS, which is used as a hole transport material in the organic light emitting device manufactured by the current solution coating method, the LUMO energy level is lower than the LUMO energy level of the organic material used as the light emitting layer material, thereby producing a high-efficiency long-life organic light emitting device. Have difficulty.

In addition, the material used in the organic light emitting device should have excellent chemical stability, charge mobility, and interface properties with an electrode or an adjacent layer. That is, the material used in the organic light emitting device should have less deformation of the material due to moisture or oxygen. In addition, it should be possible to maximize exciton formation by having a hole or electron mobility to balance the density of holes and electrons in the light emitting layer of the organic light emitting device. And, for the stability of the device, it should be possible to improve the interface with the electrode containing metal or metal oxide.

Therefore, development of a new organic material is required in the art.

Korea Patent Publication No. 2012-0112277

It is an object of the present specification to provide a fluorene derivative that can be used in an organic light emitting device, a coating composition containing the fluorene derivative, an organic light emitting device including the same, and a method for manufacturing the same.

It provides a fluorene derivative represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

Ar1 to Ar4 are the same as or different from each other, and each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

R1 to R8 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted A substituted heteroaryl group,

L is O, or-(X1) x-Y1- (Z-Y2) y- (X2) z-,

X1, X2 and Z are the same as or different from each other, and each independently, O, S, CO, SO ₂ , SO, Se, SeO ₂ , or SiR'R ”,

Y1 and Y2 are the same as or different from each other, and each independently, O, a substituted or unsubstituted arylene group, or a substituted or unsubstituted alkylene group,

R 'and R "are the same as or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

a and b are integers from 0 to 7,

x, y and z are integers of 0 or 1.

The present specification also provides a coating composition comprising the fluorene derivative.

The specification also includes a cathode; Anode; And at least one organic layer provided between the cathode and the anode, and at least one layer of the organic layer provides an organic light emitting device formed using the coating composition.

Finally, the present specification includes preparing a substrate; Forming a cathode or 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 forming the organic material layer includes forming one or more organic material layers using the coating composition. do.

The fluorene derivative according to the exemplary embodiment of the present specification is capable of a solution process, so that a large area of the device is possible. The fluorene derivative 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 low driving voltage, high luminous efficiency, and high lifespan characteristics. The organic material layer formed using the fluorene derivative according to the exemplary embodiment of the present specification has excellent chemical resistance.

In addition, as the fluorene derivative is used, solubility increases, so the solvent selection becomes wider when preparing the ink of the solution process, and there is an advantage of having appropriate coating properties by increasing the molecular weight.

1 shows an example of an organic light emitting device according to an exemplary embodiment of the present specification.
2 is a graph showing the mass spectrometry result of A1.
3 is a graph showing the results of mass spectrometry of A2.
4 is a graph showing the mass spectrometry result of A3.
5 is a voltage comparison graph of Example 1, Example 2 and Comparative Example 2.
6 is an efficiency comparison graph of Example 1, Example 2 and Comparative Example 2.
7 is a life comparison graph of Example 1, Example 2 and Comparative Example 2.

Hereinafter, the present specification will be described in detail.

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

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

In the present specification, the term “combination of these” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki form, the component It means to include one or more selected from the group consisting of.

In one embodiment of the present specification, the compound of Formula 1 is preferably a compound having solubility in a suitable organic solvent.

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

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

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

Means a site that is attached to another substituent or linkage.

In the present specification, the term “substitution” means that the hydrogen atom bound to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited if the position at which the hydrogen atom is substituted, that is, the position at which the substituent is substitutable, When two or more substituents, two or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" in this specification is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Alkyl groups; Alkoxy groups; Alkenyl group; Aryl group; And substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups, or substituted or unsubstituted with two or more substituents among the exemplified substituents. For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the halogen group is fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be a straight chain, a branched chain or a cyclic chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. Specific examples are 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, 1-octylnonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl And the like, but are not limited to these.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain.

The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyl oxy, n -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It is not limited.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, steelbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiRR'R '', wherein R, R 'and R' 'are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. Specifically, a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, 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 according to an exemplary embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 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 aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 40. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

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

,

,

및

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

,

,

And

It can be back. However, it is not limited thereto.

In the present specification, the heteroaryl group includes one or more non-carbon atoms and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the heteroaryl group has 2 to 40 carbon atoms. According to one embodiment, the carbon number of the heteroaryl group is 2 to 20. The heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrol group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Jolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe A nonthrolinyl group (phenanthroline), an isooxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the arylene group may be selected from examples of the aryl group described above, except that it is a divalent group.

In the present specification, the alkylene group may be selected from examples of the above-described alkyl group, except that it is a divalent group.

In the present specification, the cycloalkylene group may be selected from examples of the cycloalkyl group described above, except that it is a divalent group.

In the present specification, the heteroarylene group may be selected from examples of the above-described heteroaryl group, except that it is a divalent group.

According to an exemplary embodiment of the present invention, the fluorene derivative of the present invention may be represented by Formula 1 below.

[Formula 1]

According to the exemplary embodiment of the present specification, the compound of Chemical Formula 1 may include two or more triazine groups.

According to an exemplary embodiment of the present specification, the compound of Formula 1 increases solubility by including a triazine group substituted with an alkyl group

When it contains two or more triazine groups, Molecular weight 1000-2000g / mol The satisfactory, triazine structure with electronic properties occupies 50% or more of the total molecular weight, so that it has a suitable solubility and coating property as a solution OLED material.

According to an exemplary embodiment of the present invention, the fluorene derivative of the present invention may be represented by the following formula (2).

[Formula 2]

In Formula 2, Ar1 to Ar4, R1 to R8, L, and a to d are defined as in Formula 1 above.

According to one embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

According to one embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms.

According to one embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a direct bond; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group.

According to one embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a direct bond; Or an arylene group having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.

According to one embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a direct bond; A phenylene group unsubstituted or substituted with a methyl group; Or a naphthylene group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenylene group unsubstituted or substituted with a methyl group; Or a naphthylene group.

According to an exemplary embodiment of the present specification, Ar3 and Ar4 are the same as or different from each other, and each independently a phenyl group.

According to one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

According to one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; Or an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group or a silyl group.

According to one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; Or an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with a silyl group unsubstituted or substituted with an alkyl group or an aryl group.

According to one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; A phenyl group unsubstituted or substituted with a methyl group, a terbutyl group, or a trimethylsilyl group; A biphenyl group unsubstituted or substituted with a methyl group, a terbutyl group, or a trimethylsilyl group; A terphenyl group unsubstituted or substituted with a methyl group, a terbutyl group, or a trimethylsilyl group; A naphthyl group unsubstituted or substituted with a methyl group, a terbutyl group, or a trimethylsilyl group; Or a fluorene group unsubstituted or substituted with a methyl group, a terbutyl group, or a trimethylsilyl group.

According to an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, a terbutyl group, or a trimethylsilyl group; Biphenyl group; Naphthyl group; A terphenyl group unsubstituted or substituted with a terbutyl group; Or a fluorene group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, R5 and R6 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, R5 and R6 are the same as or different from each other, and each independently hydrogen; Or an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with a substituted or unsubstituted silyl group.

According to an exemplary embodiment of the present specification, R5 and R6 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, a terbutyl group, a trimethylsilyl group, or a triphenylsilyl group; Or a fluorene group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, R7 and R8 are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted silyl group.

According to an exemplary embodiment of the present specification, R7 and R8 are the same as or different from each other, and each independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R7 and R8 are the same as or different from each other, and each independently hydrogen or a methyl group.

When the R1 to R4, R7 or R8 is an alkyl group or a silyl group, solubility is improved.

According to an exemplary embodiment of the present specification, L is O, or-(X1) x-Y1- (Z-Y2) y- (X2) z-.

According to an exemplary embodiment of the present specification, L is O, -X1-Y1-X2-, -X1-Y1-Z-Y2-X2-, or -Y1-.

According to an exemplary embodiment of the present specification, X1 and X2 are the same as or different from each other, and each independently O, S, CO, SO ₂ , SO, Se, SeO ₂ , or SiR'R ".

According to an exemplary embodiment of the present specification, X1 and X2 are the same as or different from each other, and each independently O, or SiR'R ".

According to an exemplary embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and each independently O; It is a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group.

According to an exemplary embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and each independently O; A substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and each independently O; A substituted or unsubstituted methylene group; A substituted or unsubstituted hexylene group; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted fluorenylene group.

According to an exemplary embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and each independently O; A substituted or unsubstituted methylene group; A substituted or unsubstituted hexylene group; A phenylene group unsubstituted or substituted with an alkyl group; A fluorenylene group spiro-bonded with a cycloalkyl group; Or a fluorenylene group unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and each independently O; Methylene group; Hexylene group; Phenylene group; A fluorenylene group spiro-bonded with a cycloalkyl group having 5 to 10 carbon atoms; Or a fluorenylene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Z is a carbonyl group, or a sulfonyl group.

According to an exemplary embodiment of the present specification, R 'and R "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.

According to an exemplary embodiment of the present specification, R 'and R "are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. .

According to an exemplary embodiment of the present specification, R 'and R "are the same as or different from each other, and each independently a methyl group or a phenyl group.

According to an exemplary embodiment of the present specification, a and b are integers of 0 to 7.

According to an exemplary embodiment of the present specification, x, y and z is 0 or 1.

According to an exemplary embodiment of the present specification, the compound of Formula 1 may be represented by any one of the following compounds.

The compound according to one embodiment of the present specification may be prepared by a manufacturing method described later.

For example, the compound of Formula 1 may have a core structure as shown in Scheme 1 below. Substituents can be combined by methods known in the art, and the type, location or number of substituents can be changed according to techniques known in the art.

<General Manufacturing Method of Formula 1>

R1 ', R2', R5 'Ar1', Ar3 ', and Y1' are as defined for R1, R2, R5, Ar1, Ar3, and Y1 in Formula 1.

Commercially available starting materials and reactants are replaceable, and asymmetric structures can also be produced. In addition, the combination of the parts corresponding to L in Formula 1 may be different.

In one embodiment of the present specification, a coating composition including the fluorene derivative described above is provided.

In one embodiment of the present specification, the coating composition includes the fluorene derivative and a solvent.

In one embodiment of the present specification, the coating composition may further include a polymer compound. When the coating composition further includes a polymer compound, ink characteristics of the coating composition may be improved. That is, the coating composition further comprising the polymer compound may provide a suitable viscosity for coating or inkjet.

In one embodiment of the present specification, the viscosity of the coating composition is 2 cP to 15 cP. If it has a viscosity in the above range, it is easy to manufacture the device.

In one embodiment of the present specification, the molecular weight of the fluorene derivative is 1,000 g / mol to 3,000 g / mol.

In one embodiment of the present specification, the fluorene derivative may further include a thermosetting group or a photocurable group.

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

In one embodiment of the present specification, the solvent includes, for example, chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; Ether-based solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene and mesitylene; Aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, isosophone, tetralone, decalone and acetylacetone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyvalent values of ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. Alcohols and derivatives thereof; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethyl sulfoxide; And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; A solvent such as tetralin is exemplified, but a solvent capable of dissolving or dispersing the fluorene derivative according to an exemplary embodiment of the present invention is sufficient, and is not limited thereto.

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

In one embodiment of the present specification, the coating composition may further include one or more additives selected from the group consisting of a thermal polymerization initiator and a photopolymerization initiator.

As a thermal polymerization initiator, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide , Bis-3,5,5-trimethyl hexanoyl peroxide, lauryl peroxide, benzoyl peroxide, p-crol benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- (t-butyl Oxy) -hexane, 1,3-bis (t-butyl peroxy-isopropyl) benzene, t-butyl cumyl peroxide, di-tbutyl peroxide, 2,5-dimethyl-2,5- ( Dit-butyl peroxy) hexane-3, tris- (t-butyl peroxy) triazine, 1,1-dit-butyl peroxy-3,3,5-trimethyl cyclohexane, 1,1-dit -Butyl peroxy cyclohexane, 2,2-di (t-butyl peroxy) butane, 4,4-di-t-butyroxycybareric acid n-butyl ester, 2,2-bis (4, Between 4-t-butyl peroxy Rohexyl) propane, t-butylperoxyisobutylate, dit-butyl peroxy hexahydro terephthalate, t-butyl peroxy-3,5,5-trimethylhexaate, t-butylperoxybenzoate, di peroxides such as t-butyl peroxy trimethyl adipate, or azo systems such as azobis isobutylnitrile, azobisdimethylvaleronitrile, and azobis cyclohexyl nitrile, but are not limited thereto.

Examples of the photopolymerization initiator include diethoxy acetophenone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 4- (2-hydroxy ethoxy). Phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl Propan-1-one, 2-methyl-2-morpholino (4-methyl thiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime Acetophenone-based or ketal-based photopolymerization initiators such as, benzoin, benzoin methyl ether, benzoin ether ether, benzoin isobutyl ether, benzoin isopropier ether, benzoin ether, etc. Benzophenone-based photopolymerization initiators such as benzophenone, 4-hydroxybenzophenone, 2-benzoyl naphthalene, 4-benzoyl biphenyl, 4-benzoyl phenyl ether, acrylate benzophenone, 1,4-benzoyl benzene, etc., 2-isopropyl thioxanthone, 2-cle Thioxanthone-based photopolymerization initiators such as rotoxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, and other photopolymerization initiators include ethyl anthraquinone, 2 , 4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, bis (2,4- Dimethoxy benzoyl) -2,4,4-trimethyl pentylphosphine oxide, methyl phenyl glyciokistelyl, 9,10-phenanthrene, acridine compounds, triazine compounds, imidazole compounds, and the like have. Moreover, what has a photopolymerization promoting effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyl diethanol amine, ethyl 4-dimethylamino benzoate, isoamyl 4-dimethylamino benzoate, ethyl benzoate (2-dimethylamino), 4,4'-dimethylaminobenzophenone, and the like, It is not limited.

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

In one embodiment of the present specification, the cathode; Anode; And the cathode. It includes at least one layer of an organic material provided between the anodes, and at least one layer of the organic material layer is formed using the coating composition or a cured product thereof.

In one embodiment of the present specification, the organic light emitting device includes the fluorene derivative of Formula 1 in the light emitting layer.

In one embodiment of the present specification, the organic light emitting device includes the fluorene derivative of Formula 1 as a host in the light emitting layer.

In one embodiment of the present specification, the organic light emitting device further includes a light emitting material such as a fluorene derivative of Formula 1 and a metal complex in the light emitting layer.

The metal complex may be an iridium-based complex, but is not limited thereto. For an iridium complex, Ir (L1) a '(L2) b' (L3) c '(a' + b '+ c' = 3, a ', b' and c 'are integers of 0-3) It has a structure. L1 is an anionic monovalent bidentate cyclometalating ligand and is linked with a carbon and nitrogen atom, L2 is a monovalent anionic bidentate ligand, not linked with carbon, and L3 is a single letter Ligand (monodentate ligand).

L1 is phenylpyridines, phenylquinolines, phenylpyrimidines, phenylpyrazoles, thienylpyridines, thienylquinolines, and thienyl pyridines Thienylpyrimidines may be used, but the present invention is not limited thereto.

L2 is an atom in which N, O, P, and S are mainly coordinated, and forms a pentagonal or hexagonal ring with iridium. Suitable coordinating groups include amino groups, imino groups, amido groups, and alkoxide groups. Carboxylate groups, phosphine groups, thiolate groups, and the like are possible, but are not limited thereto.

L3 is anionic or nonionic, and anionic ligands have C, O, and S as coordinating atoms, specifically carboxylate, thiocarboxylate ( thiocarboxylate, dithiocarboxylate, sulfonate, thiolate, carbamate, dithiocarbamate, thiocarbazone anions, sulfonamide (sulfonamide), anions, etc. are possible, but are not limited thereto.

The iridium complex can be represented by the following formula.

In one embodiment of the present specification, the organic light emitting device includes a light emitting material such as a metal complex in the light emitting layer: the fluorene derivative in a weight ratio of 1: 100 or 100: 1.

In one embodiment of the present specification, the organic light emitting device includes a light emitting material such as a metal complex in the light emitting layer: the fluorene derivative in a weight ratio of 1: 100 to 20: 1.

In another embodiment, the organic light emitting device includes a light emitting material such as a metal complex in the light emitting layer: the fluorene derivative in a weight ratio of 1: 100 or 1: 1.

In one embodiment of the present specification, the organic light emitting device includes a light emitting material such as a metal complex in the light emitting layer: the fluorene derivative in a weight ratio of 5:95 to 20:80.

In an exemplary embodiment of the present specification, the organic light emitting device may include a coating composition comprising the fluorene derivative of Formula 1, or a cured product thereof in a hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection. You can.

In one embodiment of the present specification, the organic light emitting device may include a hole transport layer, a hole injection layer, or a layer that simultaneously performs hole transport and hole injection.

In one embodiment of the present specification, the organic light emitting device may include a hardened material of the coating composition containing the fluorene derivative of Chemical Formula 1 in a hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection. .

In one embodiment of the present specification, the organic light emitting device includes a coating composition comprising the fluorene derivative of Formula 1, or a cured product thereof in an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport. can do.

In one embodiment of the present specification, the organic light emitting device may include a coating composition comprising the fluorene derivative of Formula 1, or a cured product thereof in the electron blocking layer.

In one embodiment of the present specification, the organic light emitting device may include a coating composition including the fluorene derivative of Formula 1, or a cured product thereof in the electrolytic barrier layer.

In one embodiment of the present specification, the organic light emitting device is a light emitting layer, a hole injection layer, a hole transport layer. It further includes at least one layer 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, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In another 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 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 the structure of an organic light emitting device in which an anode 201, a hole injection and transport layer 301, a light emitting layer 401, an electron transport layer 501, and a cathode 601 are sequentially stacked on a substrate 101. have.

1 illustrates an organic light emitting device 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 made of materials and methods known in the art, except that at least one layer of the organic material layer is formed using a coating composition containing the fluorene derivative or a cured product thereof.

For example, the organic light emitting device of the present specification can be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, an anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. And, after forming a hole injection layer, a hole transport layer, an organic material layer including a light emitting layer and an electron transport layer, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be formed 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 or a cured product thereof.

Specifically, in one embodiment of the present specification, preparing a substrate; Forming a cathode or 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.

The step of forming one or more layers of the organic material layer using the coating composition may include a drying step after applying the coating composition. If necessary, the drying step may include a curing step.

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 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.

Since the coating composition according to one embodiment of the present specification has a structural characteristic, a solution process is suitable, and thus can be formed by a printing method, there is a time and cost-effective economic effect when manufacturing a device.

In one embodiment of the present specification, the step of forming an organic material layer using the coating composition includes heat treatment or vacuum drying. Residual solvent is removed through the heat treatment or vacuum drying.

In one embodiment of the present specification, the step of forming an organic material layer using the coating composition includes vacuum drying.

In one embodiment of the present specification, the heat treatment or vacuum drying may include a curing step.

In one embodiment of the present specification, the coating composition containing the fluorene derivative may use a coating composition dispersed in a polymer binder.

In one embodiment of the present specification, as the polymer binder, it is preferable that the charge transport is not extremely inhibited, and that the absorption of visible light is not strong is preferably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylenevinylene) and derivatives thereof, poly (2,5-thienylenevinylene), and And derivatives thereof, polycarbonate, polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like .

As the anode material, a material having a large work function is preferably used to facilitate hole injection 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 SNO2: combination of metal and oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, but are not limited thereto.

The cathode 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; There is a multilayer structure material such as LiF / Al or LiO2 / Al, but is not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in the light emitting layer A compound that prevents migration of the excited excitons to the electron injection layer or the electron injection material, and has excellent thin film formation ability is preferred. 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 matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and 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. As a hole transport material, the hole is transported to the light emitting layer by transporting holes from an anode or a hole injection layer, and the mobility of holes is large. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq3); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic compounds include fluorene derivatives, dibenzofuran derivatives, and ladder forms. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes arylamino groups such as pyrene, anthracene, chrysene, periplanten, and the substituted or unsubstituted styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transporting material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons This is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, 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) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The hole blocking layer is a layer that prevents the cathode 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 are not limited thereto.

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

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

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not construed as being 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.

According to another exemplary embodiment, the compound of Formula 1 may be represented by the following structural formulas.

< Synthetic example >

One. A1 of  synthesis

10 g of A1-2 and 10.2 g of A1-3 were added to a 500 mL round bottom flask (RBF), followed by 1.2 g of Pd (PPh ₃ ) ₄ . The mixture was vacuumed and refilled with nitrogen. After repeating this process 3 times, 210 mL of tetrahydrofuran (THF) was added. After stirring, all solids were dissolved, and 2 mL of 2 MK ₂ CO ₃ (aq) was added. The mixture was stirred at 60 ° C for 12 hours.

200 mL of NH ₄ Cl (aq) was added to the resulting mixture, and extracted with 200 mL of EtOAc (x2). The obtained organic layer was dried over MgSO ₄ , filtered, and concentrated. The obtained mixture was dissolved in DCM, poured into EtOH to solidify, and the obtained solid was recrystallized using DCM / EtOH to obtain 10 g of A1-1.

After dissolving 3.39 g of A1-1 in 50 mL of Acetone, 1.3 g of potassium carbonate was added. After stirring for 5 minutes, 0.37 mL of dibromohexane was added. The mixture was stirred with reflux for 3 days. 50 mL of NH ₄ Cl (aq), DCM (200 mL) was added to the obtained mixture, and after obtaining an organic layer, SiO ₂ (50 g) was added, followed by stirring for 30 minutes and filtering. The resulting solution was concentrated, dissolved in DCM, recrystallized with EtOH, and 2 g of A1 was obtained.

2 is a graph showing the mass spectrometry result of A1.

2. A2 of  synthesis

After dissolving 2 g of A1-1 in 10 mL of NMP, 1 g of potassium carbonate was added. Thereafter, the mixture was heated to 150 ° C. and stirred for 2 days. EtOH was added to the resulting mixture to filter the resulting solid, and the solid was dissolved in DCM, purified by SiO ₂ column, and recrystallized using a DCM / Hexane mixed solution to obtain 1 g of A2.

3 is a graph showing the results of mass spectrometry of A2.

3. A3 of  synthesis

After dissolving 1 g of A3-1 in 6 mL of NMP, 0.4 g of potassium carbonate was added. After adding 130 mg of A3-1, the mixture was heated at 150 ° C. and stirred for 2 days. The resulting mixture was filtered by adding EtOH to the obtained mixture, and the solid was dissolved in DCM, purified by SiO ₂ column, and recrystallized using a DCM / Hexane mixed solution to obtain 0.5 g of A3.

4 is a graph showing the mass spectrometry result of A3.

Experimental Example 1. Measurement of solubility of synthesized materials

1900 mg of toluene was added to 100 mg of Compound A1 of the Synthesis Example, and heated to 60 ° C. using an oil bath. After the solids were all melted, they were cooled to room temperature and observed to precipitate after an hour, and observed again after a week. The prepared solution was not precipitated even after a week, but a clear solution was maintained.

Experimental example  2.

It is the same as in Experimental Example 1 except that Compound A2 was used instead of Compound A1. The prepared solution was not precipitated even after a week, and a clear solution was maintained.

Through Experimental Examples 1 and 2, it was confirmed that the compound of Formula 1 has an appropriate solubility as a material for solution processing.

< Example >

Example  One

A glass substrate coated with a thin film of indium tin oxide (ITO) at a thickness of 50 nm was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as a detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner. In addition, after the substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

AI4083 was formed on the ITO transparent electrode thus prepared to form a 60 nm hole injection and transport layer under the process conditions of Table 1 below.

matter Coating speed time Soft baking Hard baking AI4083 1000 rpm 60s 80 ℃, 2min 120 ℃, 15min

Poly (9,9-di-n-octylfluorenyl-2,7-diyl) (sigma Aldrich) on the hole injection and transport layer ) And Compound A1 of the above Synthesis Example and the metal complex D41 were prepared by 0.5% by weight of a toluene solution at 91: 9 parts by weight, spin-coated at 5000 rpm, baked at 80 ° C for 2 minutes, and baked at 120 ° C for 30 minutes. ) To form a light emitting layer having a thickness of 55 nm.

After drying it at 130 ° C. for 10 minutes in a nitrogen gas atmosphere, lithium fluoride (LiF) was deposited to a film thickness of about 1 nm, and finally aluminum was deposited to a film thickness of 100 nm to form a negative electrode.

In the above process, the deposition rate of lithium fluoride of the negative electrode was 0.3 Å / sec and aluminum of 2 Å / sec, and the vacuum degree during deposition was maintained at 2 ⅹ10 ^-7 to 5 ⅹ10 ^-6 torr, thereby producing an organic light emitting device. .

Example  2

The experiment was conducted in the same manner as in Example 3, except that Compound A2 was used instead of Compound A1 in Example 1.

< Comparative example >

Comparative example  One.

Comparative Example B1 was used instead of A1 in Experimental Example 1. Although it was tested, it could not be dissolved by adding an additional 2000 mg of toluene. However, it was deposited as a result of observation for one week at room temperature.

From the above results, it can be seen that the compound of the present invention has a good solubility of 5 wt / wt% or more and does not precipitate even after being stored for a long time, and thus is suitable as a material for solution processing.

Comparative example  2

In Example 1, the same experiment was carried out except that Comparative Compound B1 was used instead of A1.

The results of Examples 1 and 2 and Comparative Example 2 are shown in FIGS. 5 to 7.

5 is a voltage comparison graph of Example 1, Example 2 and Comparative Example 2. Through this, it can be seen that Example 1 and Example 2 are driven at a lower voltage than Comparative Example 2.

6 is an efficiency comparison graph of Example 1, Example 2 and Comparative Example 2. Through this, it was confirmed that Example 1 and Example 2 emit light with higher efficiency than Comparative Example 2.

7 is a life comparison graph of Example 1, Example 2 and Comparative Example 2. Through this, it can be seen that Example 1 and Example 2 have a longer life than Comparative Example 2.

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

Claims (15)

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

In Chemical Formula 1,
Ar1 to Ar4 are the same as or different from each other, and each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,
R1 to R8 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted A substituted heteroaryl group,
L is O, or-(X1) x-Y1- (Z-Y2) y- (X2) z-,
X1, X2 and Z are the same as or different from each other, and each independently, O, S, CO, SO ₂ , SO, Se, SeO ₂ , or SiR'R ”,
Y1 and Y2 are the same as or different from each other, and each independently, O, a substituted or unsubstituted arylene group, or a substituted or unsubstituted alkylene group,
R 'and R "are the same as or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,
a and b are integers from 0 to 7,
x, y and z are 0 or 1.
The method according to claim 1, wherein Formula 1 is a fluorene derivative represented by Formula 2:
[Formula 2]

In Chemical Formula 2
R1 to R8, Ar1 to Ar4, L, a and b are as defined in Chemical Formula 1.
The method according to claim 1, wherein Ar1 and Ar2 are the same as or different from each other, and each independently a phenylene group unsubstituted or substituted with a methyl group; Or a fluorene derivative which is a naphthylene group.
The method according to claim 1, wherein Ar3 and Ar4 are the same as or different from each other, and each is a fluorene derivative independently of a phenylene group.
The method according to claim 1, wherein R1 to R4 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, a terbutyl group, or a trimethylsilyl group; Biphenyl group; Naphthyl group; A terphenyl group unsubstituted or substituted with a terbutyl group; Or a fluorene derivative which is a fluorene group unsubstituted or substituted with a methyl group.
The method according to claim 1, wherein R5 and R6 are the same as or different from each other, and each independently a methyl group, a terbutyl group, a trimethylsilyl group, or a phenyl group unsubstituted or substituted with a triphenylsilyl group; Or a fluorene derivative which is a fluorene group unsubstituted or substituted with a methyl group.
The fluorene derivative of claim 1, wherein the fluorene derivative is any one of the following compounds:

The fluorene derivative of claim 1, wherein the fluorene derivative has a molecular weight of 1,000 g / mol to 3,000 g / mol. A coating composition comprising the fluorene derivative according to claim 1. The coating composition of claim 9, wherein the coating composition further comprises a light emitting material such as a metal complex. The coating composition according to claim 9, wherein the coating composition is a light emitting material such as a metal complex: the fluorene derivative is mixed in a weight ratio of 1: 100 or 1: 1. Cathode;
Anode; And
It includes at least one organic layer provided between the cathode and the anode,
At least one layer of the organic layer comprises the coating composition of claim 9 or a cured product thereof. The method according to claim 12, The organic layer is a hole transport layer, a hole injection layer, or a hole injection layer and a hole injection and hole transport layer containing the cured product of the coating composition at the same time. Preparing a substrate;
Forming a cathode or 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,
The step of forming the organic material layer comprises forming one or more organic material layers using the coating composition of claim 9. The method of claim 14, wherein the forming of the organic material layer formed by using the coating composition includes a drying step after applying the coating composition.

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