KR102101058B1 - 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, organic light-emitting device using the same, and manufacturing method thereof {FLUORENE DERIVATIVES, ORGANIC LIGHT EMITTING DIODE USING THE SAME AND METHOD OF MANUFACTURING THE SAME}

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. An 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

An object of the present specification is to provide a fluorene derivative usable in an organic light emitting device and an organic light emitting device including the same.

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

[Formula 1]

In Chemical Formula 1,

L1 to L3 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; A substituted or unsubstituted cycloalkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar1 is a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

L4 is a substituted or unsubstituted arylene group,

X1 and X2 are the same as or different from each other, and each independently hydrogen; Thermosetting group; Or a photocurable group, at least one of X1 and X2 being a thermosetting group; Or a photocurable group,

A is hydrogen; Or NRR ',

R and R 'are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

n1 is an integer from 0 to 4,

n2 is an integer from 0 to 3,

When n1 and n2 are each 2 or more, the substituents in parentheses are the same as or different from each other.

The present specification 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 and membrane retention.

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 lowering the melting point and curing temperature.

1 shows an example of an organic light emitting device according to an exemplary embodiment of the present specification.
2 is a view showing driving voltages according to current densities of the organic light emitting devices manufactured in Examples 1 to 3 and Comparative Example 1.
3 is a view showing the power efficiency according to the current density of the organic light emitting device prepared in Examples 1 to 3 and Comparative Example 1.
4 is a view showing luminance values of the organic light emitting devices manufactured in Examples 1 to 3 and Comparative Example 1.
5 is a diagram showing NMR data of Chemical Formulas 1-2-13.

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.

One embodiment of the present specification provides a fluorene derivative represented by Chemical Formula 1.

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

In the present specification, “thermosetting group or photocurable group” may mean a reactive substituent that crosslinks between compounds by exposure to heat and / or light. Cross-linking may be generated by heat-radiation or light irradiation, carbon-carbon multiple bonds, and radicals formed as the cyclic structures are decomposed and linked.

In one embodiment of the present specification, the thermosetting group and the photocurable group are any of the following structures.

In the above structure,

R4 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,

A1 to A3 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

In an exemplary embodiment of the present specification, in the case of a fluorene derivative containing a thermosetting group or a photocurable group, an organic light emitting device can be manufactured by a solution coating method, which is economical in time and cost.

In addition, when a coating layer is formed by using a coating composition comprising a fluorene derivative containing a thermosetting group or a photocurable group, since the crosslinking is formed by heat or light, the thermosetting group or photocurable group is further added to the top of the coating layer. When the layers are stacked, the fluorene derivative contained in the coating composition is prevented from being washed out by a solvent, so that an additional layer can be stacked on the top while maintaining the coating layer.

In addition, when a coating layer is formed by forming a crosslinking group by thermosetting or photocuring groups, chemical resistance to the solvent of the coating layer is increased, and a film retention rate is high.

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.

According to an exemplary embodiment of the present specification, in the case of a fluorene derivative crosslinked by heat treatment or light irradiation, a plurality of fluorene derivatives are crosslinked and provided in the organic light emitting device in the form of a thin film, thereby having excellent thermal stability. Therefore, the organic light emitting device using the fluorene derivative according to the exemplary embodiment of the present specification has an excellent lifespan characteristic effect.

In addition, since the fluorene derivative according to an exemplary embodiment of the present specification includes an amine structure in a core structure, it may have an appropriate energy level and a band gap as a hole injection, hole transport material, or light emitting material in an organic light emitting device. In addition, by controlling the substituents of the compound of Formula 1 according to an exemplary embodiment of the present specification, it is possible to finely adjust an appropriate energy level and a band gap, and improve the interfacial properties between organic materials, resulting in low driving voltage and high luminous efficiency. It is possible to provide an organic light-emitting device having.

As in the present invention, when a coating layer is formed using a polymer containing a fluorene derivative having a curable group, compared to a case where a single molecule fluorene derivative containing a thermosetting group or a photocurable group is used, the content of the curing group is There is a problem that it is difficult to harden at a desired position because there is a limitation and it is fixed to a long main chain.

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 hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Alkyl groups; Alkoxy groups; Alkenyl group; Amangi; 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, branched chain or cyclic chain,

The number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary 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, i-propyloxy, 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 may be, but is not limited to this.

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 this specification, the number of carbon atoms in the amine group is not particularly limited, but is preferably 1 to 30. The amine group may be substituted with an N atom, an aryl group, an alkyl group, an alkenyl group, an arylalkyl group, and a heteroaryl group, and specific examples of the amine group are methylamine group, dimethylamine group, ethylamine group, and diethylamine group. , Phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, Triphenylamine groups, and the like, but are not limited to these.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, and 9-methyl-anthra Senylamine, diphenyl amine group, phenyl biphenylamine group, phenyl naphthyl amine group, dibiphenyl amine group, N-phenyl fluoreneamine group, N-biphenyl fluoreneamine group, N, N-diphenyl fluorene Amine groups, ditolyl amine groups, phenyl tolyl amine groups, carbazole and triphenyl amine groups, but are 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, 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 Nanthrolyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group and 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.

In one embodiment of the present specification, A in Chemical Formula 1 is hydrogen; Or NRR ', R and R' are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

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 Formulas 2 and 3,

R1, R2, n1, n2, L1 to L4, X1, X2 and Ar1 are the same as defined in Chemical Formula 1,

Ar2 and Ar3 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, L3 is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

According to an exemplary embodiment of the present specification, L3 is a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L3 is a direct bond; An arylene group having 6 to 60 carbon atoms; Or a heteroarylene group having 2 to 60 carbon atoms.

According to another exemplary embodiment, L3 is a direct bond; It is an arylene group having 6 to 20 carbon atoms.

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

In another exemplary embodiment, L3 is a direct bond.

In one embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formula 4 or Chemical Formula 5.

[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,

R1, R2, n1, n2, L1, L2, X1, X2, Ar1, L4 and A are the same as defined in Formula 1,

R3 is hydrogen; heavy hydrogen; Silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

n3 is an integer from 0 to 4.

According to the exemplary embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

According to another exemplary embodiment, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 20 carbon atoms; Or an aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, R1 to R3 are hydrogen.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently substituted or unsubstituted alkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently substituted or unsubstituted alkylene group having 1 to 40 carbon atoms; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

According to another exemplary embodiment, L1 and L2 are the same as or different from each other, and each independently an alkylene group having 1 to 40 carbon atoms; An arylene group having 6 to 60 carbon atoms; Or a heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L1 and L2 are the same as or different from each other, and each independently an alkylene group having 1 to 20 carbon atoms; An arylene group having 6 to 20 carbon atoms; Or a heteroarylene group having 2 to 20 carbon atoms.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently an arylene group having 6 to 20 carbon atoms.

According to another exemplary embodiment, L1 and L2 are phenylene groups.

In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently an alkylene group having 1 to 20 carbon atoms.

In another exemplary embodiment, L1 and L2 are a methylene group, an ethylene group, or a propylene group.

In another exemplary embodiment, L1 and L2 are methylene groups.

In one embodiment of the present specification, X1 and X2 are the same as or different from each other, and each independently a thermosetting group or a photosetting group.

In one embodiment of the present specification, L4 is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, L4 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

In another exemplary embodiment, L4 is an arylene group having 6 to 20 carbon atoms.

In another exemplary embodiment, L4 is a phenylene group; Biphenylene group; Terphenylene group; Naphthylene group; Or a substituted or unsubstituted fluorenylene group.

According to another exemplary embodiment, L4 is a phenylene group; Or a biphenylene group.

In one embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In another exemplary embodiment, Ar1 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In another exemplary embodiment, Ar1 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted fluorenyl group.

According to another exemplary embodiment, Ar1 is a phenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; A biphenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; A naphthyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; Or a fluorenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group.

According to another exemplary embodiment, Ar1 is a phenyl group substituted with a phenyl group, a biphenyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a diphenylamine group, or a carbazole group.

In one embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In another exemplary embodiment, Ar2 and Ar3 are the same as or different from each other, and each independently substituted or unsubstituted phenyl group, substituted or unsubstituted, biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted It is a substituted fluorenyl group, a substituted or unsubstituted dibenzofuran group, a substituted or unsubstituted dibenzothiophene group, or a substituted or unsubstituted carbazole group.

In another exemplary embodiment, Ar2 and Ar3 are the same as or different from each other, and each independently a phenyl group, a phenyl group substituted with a vinyl group, a phenyl group substituted with an isopropenylphenylamine group, or a phenyl group substituted with a phenylpyridylamine group, A phenyl group substituted with a diphenylamine group, a phenyl group substituted with a carbazole group, a biphenyl group, a biphenyl group substituted with a diphenylamine group, a biphenyl group substituted with a 9,9-dimethylfluorenylphenylamine group, a naphthyl group, and a dibenzofuran group , Dibenzothiophene group, N-phenylcarbazole group, N-ethylcarbazole group, or 9,9-dimethylfluorenyl group.

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

The compound according to the exemplary 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 prepared in Preparation Example as follows. Substituents can be combined by methods known in the art, and the type, location, or number of substituents can be varied according to techniques known in the art.

In one embodiment of the present specification, a coating composition including the above-described fluorene derivative 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 one or two types of compounds selected from the group consisting of a compound having a thermosetting group or a photocurable group introduced into a molecule and a polymer compound.

In one embodiment of the present specification, the coating composition may further include a compound having a thermosetting group or a photocurable group introduced into the molecule. When the coating composition further includes a compound in which a thermosetting group or a photocurable group is introduced into the molecule, the degree of curing of the coating composition may be further increased.

In one embodiment of the present specification, the molecular weight of a compound in which a thermosetting group or a photocurable group is introduced into a molecule is 100 g / mol to 5,000 g / mol.

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 polymer compound is 10,000 g / mol to 1,000,000 g / mol.

In one embodiment of the present specification, the polymer compound 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 exemplary embodiment, the solvent may be used alone or as a mixture of two or more solvents.

In one embodiment of the present specification, the coating composition may further include one or more additives selected from the group consisting of a thermal polymerization initiator and a photo polymerization 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-based compound, triazine-based compound, imidazole-based compound, 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.

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

In the present specification, the p-doped material means a material that makes the host material have p-semiconductor properties. The p-semiconductor property means a property in which holes are injected or transported at a HOMO (highest occupied molecular orbital) energy level, that is, a property of a material having high hole conductivity.

In one embodiment of the present specification, the p-doped material may be represented by any one of the following Chemical Formulas 2-1 to 4-1, but is not limited thereto.

[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

In the present specification, the p-doped material is sufficient as long as it is a material having p-semiconductor properties, and one or two or more types may be used, and the type of the p-doped material is not limited.

In one embodiment of the present specification, the content of the p-doped material is 0% to 50% by weight based on the fluorene derivative of Formula 1 above.

In one embodiment of the present specification, the content of the p-doped material includes 0 to 30% by weight based on the total solid content of the coating composition. Of this specification

In one embodiment, the content of the p-doped material preferably includes 1 to 30% by weight based on the total solids content of the coating composition, and in another embodiment, the content of the p-doped material is It is more preferable to include 10 to 30% by weight based on the total solids content of the coating composition.

In another embodiment, the coating composition is a single molecule comprising a thermosetting group or a photocurable group; Or it may further include a single molecule containing a terminal group capable of forming a polymer by heat. Single molecule containing a thermosetting group or a photocurable group as described above; Alternatively, the molecular weight of a single molecule containing a terminal group capable of forming a polymer by heat may be 2,000 g / mol or less.

In one embodiment of the present specification, the coating composition has a molecular weight of 2,000 g / mol or less, a single molecule comprising a thermosetting group or a photocurable group; Or it further includes a single molecule containing a terminal group capable of forming a polymer by heat.

A single molecule comprising the thermosetting group or photocurable group; Or a single molecule containing a terminal group capable of forming a polymer by heat includes aryl of phenyl, biphenyl, fluorene, and naphthalene; Arylamine; Or it may mean a single molecule in which fluorene is substituted with a thermosetting group or a photocurable group or a terminal group capable of forming a polymer by heat.

In another exemplary embodiment, the viscosity of the coating composition is 2 cP to 15 cP.

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 one or more organic material layers provided between the cathode and the anode, and one or more layers of the organic material layers are formed by using the coating composition, thereby including a cured product of the coating composition. The cured product of the coating composition means a state in which the coating composition is cured by heat treatment or light treatment.

In one embodiment of the present specification, the organic material layer including the cured product of the coating composition is a hole transport layer, a hole injection layer, or a layer that simultaneously performs hole transport and hole injection.

In another exemplary embodiment, the organic material layer formed using the coating composition is a light emitting layer.

In another exemplary embodiment, the organic material layer including the cured product of the coating composition is a light emitting layer, and the light emitting layer includes the fluorene derivative as a host of the light emitting layer.

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

The organic material layer of the organic light emitting device of the present specification may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer 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, an organic light emitting device in which an anode 201, a hole injection layer 301, a hole transport layer 401, a light emitting layer 501, an electron transport layer 601, and a cathode 701 are sequentially stacked on a substrate 101 The structure of is illustrated.

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 manufactured by materials and methods known in the art, except that at least one layer of the organic material layer is formed using the coating composition containing the fluorene derivative.

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 for manufacturing an organic light emitting device formed using the coating composition.

Specifically, in one embodiment of the present specification, preparing a substrate; Forming a cathode or anode on the substrate; Forming one or more organic material layers on the cathode or anode; And forming an anode or a cathode on the organic material layer, wherein at least one layer of the organic material layer is formed using the coating composition.

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

In another embodiment, the organic 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 property, a solution process is suitable, and thus can be formed by a printing method, it is economical in time and cost when manufacturing the device.

In one embodiment of the present specification, forming an organic material layer formed using the coating composition may include coating the coating composition on the cathode or anode; And heat-treating or photo-treating the coated coating composition.

In one embodiment of the present specification, the heat treatment temperature in the heat treatment step is 85 ° C to 300 ° C.

In another exemplary embodiment, the heat treatment time in the heat treatment step may be 1 minute to 1 hour.

In one embodiment of the present specification, when the coating composition does not contain an additive, heat treatment is performed at a temperature of 100 ° C to 300 ° C, and crosslinking is preferably performed, and crosslinking proceeds at a temperature of 150 ° C to 250 ° C. It is more preferable to be. In addition, the coating composition of the present specification may further include an initiator, but it is more preferably not used.

In the case of including the heat treatment or the photo-treatment step in the step of forming the organic layer formed using the coating composition, a plurality of fluorene derivatives included in the coating composition may form a crosslink to provide an organic layer containing a thinned structure. . In this case, when laminating another layer on the surface of the organic layer formed using the coating composition, it can be prevented from being dissolved by a solvent, morphologically affected or decomposed.

Therefore, when the organic layer formed by using the coating composition is formed by including a heat treatment or photo-treatment step, resistance to solvent increases, and a solution deposition and crosslinking method can be repeatedly performed to form a multi-layer, and the stability is increased to increase device stability. Life characteristics can be increased.

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

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 Derivatives thereof, polycarbonate, polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

In addition, the fluorene derivative according to the exemplary embodiment of the present specification may include fluorene and an amine group, so that the organic material layer may include the fluorene derivative alone, and the coating composition containing the fluorene derivative may be thinned through heat treatment or light treatment. It can also proceed, and can be included as a copolymer using a coating composition mixed with other monomers. In addition, by using a coating composition mixed with other polymers, it may be included as a copolymer, or may be included as a mixture.

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, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types 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 Chemical Formula 1 may be represented by the following structural formulas.

< Manufacturing example >

Manufacturing example  1-1-1. Preparation of Formula 1-2-1

                                             [Formula A-1-1]

2-bromo-9H-fluorene (5g, 20.4mmol) was dissolved in tetrahydrofuran (200ml), sodium hydroxide (1.67g, 41.8mmol), benzyl trimethyl ammonium chloride (465mg, 2.04mmol) Put it, stir at room temperature for 1 hour, add 1- (chloromethyl) -4-vinylbenzene (8.29g, 48.9mmol) at 0 ° C, raise to room temperature, and stir for 16 hours under a nitrogen atmosphere. The reaction is terminated by adding 1N HCl (10 ml). After extracting the organic layer using methylene chloride, the column was separated with a solvent of normal-hexane / ethyl acetate = 1: 20, followed by vacuum drying to obtain Chemical Formula A-1-1. (7,2g, yield 74%)

MS: [M + H] ⁺ = 477

                                             [Formula A-2-1]

2-Bromo-9H-fluorene (20g, 1eq, 81.592mmol) (4-chlorophenyl) boronic acid (15.31g, 97.910mmol), Pd (PPh ₃ ) ₄ (0.942g, 0.816mmol), K ₂ CO ₃ (33.83 g, 244.776 mmol) was added to 500 ml of tetrahydrofuran (THF), and refluxed at 80 ° C. for 16 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted using methylene chloride (MC). Recrystallization using methylene chloride and ethanol gave an intermediate of formula A-2-1. (18 g, 80% yield) MS: [M + H] ⁺ = 277

NaOH (2.96g, 74.071mmol) and benzyltrimethylammonium chloride (820mg, 3.613mmol) were dissolved in 400ml of tetrahydrofuran (THF) in this intermediate (10g, 36.132mmol), followed by 4-chloromethylstyrene (14.09g, 3.613mmol) ) Was added and stirred at room temperature for 16 hours, and then 1N HCl (10 ml) was added to terminate the reaction. After extracting the organic layer using methylene chloride, the column was separated with a solvent of normal-hexane / ethyl acetate-1: 25, and then dried in vacuo to obtain Chemical Formula A-2-1 (10 g, yield 54%).

MS: [M + H] ⁺ = 509

[Formula A-1-1] [Formula 1-2-1]

Formula A-1-1 (4g, 8.378mmol), (4- (diphenylamino) phenyl) boronic acid (Formula B-2-1, 2.9g, 10.054mmol) in tetrahydrofuran (THF) (200ml) After melting, potassium carbonate (3.48g, 25.134mmol) and Pd (PPh ₃ ) ₄ (986mg, 0.838mmol) were added and refluxed at 80 ° C for 17 hours. The organic layer was extracted using methylene chloride. The reaction solution was concentrated, dissolved in methylene chloride (MC), and recrystallized with ethyl alcohol (EtOH) to obtain Chemical Formula 1-2-1 (3 g, yield 56%). MS: [M + H] ⁺ = 642

Manufacturing example  1-1-2. Preparation of Formula 1-2-2

[Formula A-1-1] [Formula 1-2-2]

In the preparation example of Chemical Formula 1-2-1, Chemical Formula 1-2-2 was obtained by reacting in the same manner, except that Chemical Formula B-2-4 was used instead of Chemical Formula B-2-1. MS: [M + H] ⁺ = 794

Manufacturing example  1-1-3. Preparation of Formula 1-2-3

[Formula A-1-1] [Formula A-2-1] [Formula 1-2-3]

In the preparation example of Chemical Formula 1-2-1, Chemical Formula was reacted in the same manner except that Chemical Formula A-2-1 was substituted for Chemical Formula A-1-1 and B-3-1 was substituted for Chemical Formula B-2-1. 1-2-3 was obtained. MS: [M + H] ⁺ = 809

Manufacturing example  1-1-4. Preparation of Formula 1-2-4

[Formula A-1-1] [Formula A-2-1] [Formula A-3-1]

[Formula A-3-1] [Formula A-4-1]

[Formula 1-2-4]

In the preparation example of Chemical Formula 1-2-1, Chemical Formula A-4-1 instead of Chemical Formula A-1-1, and (4- (diphenylamino) phenyl) boronic acid instead of Aniline were used. Reaction was carried out to obtain Formula 1-2-4. MS: [M + H] ⁺ = 885

Manufacturing example  1-1-5. Preparation of Formula 1-2-5

[Formula A-2-1] [Formula 1-2-5]

In the preparation example of Chemical Formula 1-2-1, Chemical Formula 1-2- was reacted in the same manner, except that Chemical Formula A-2-1 was substituted for Chemical Formula A-1-1 and Chemical Formula B-1-28 was substituted for aniline. 5 was obtained. MS: [M + H] ⁺ = 1052

Manufacturing example  1-1-6. Preparation of Formula 1-2-6

[Formula A-3-1] [Formula A-4-1] [Formula 1-2-6]

In the preparation example of Chemical Formula 1-2-1, Chemical Formula 1-2- was reacted in the same manner except that Chemical Formula A-4-1 was substituted for Chemical Formula A-1-1 and Chemical Formula B-2-5 was substituted for aniline. 6 was obtained. MS: [M + H] ⁺ = 1050

Manufacturing example  1-1-7. Preparation of Formula 1-2-7

[Formula 1-2-7]

In the preparation example of Chemical Formula 1-2-1, the reaction was performed in the same manner as Chemical Formula 1-2-7 except that A-2-1 instead of Formula A-1-1 and B-1-31 instead of Aniline were used. Got MS: [M + H] ⁺ = 961

Manufacturing example  1-1-8. Preparation of Formula 1-2-8

[Formula A-2-1] [Formula 1-2-8]

In the preparation example of Chemical Formula 1-2-1, it was reacted in the same manner as Chemical Formula 1-2-8 except that A-2-1 instead of Formula A-1-1 and B-1-32 instead of Aniline were used. Got MS: [M + H] ⁺ = 1077

Manufacturing example  1-1-9. Preparation of Formula 1-2-9

[Formula A-2-1] [Formula 1-2-9]

In the preparation example of Chemical Formula 1-2-1, it was reacted in the same manner as Chemical Formula 1-2-9 except that A-2-1 instead of Formula A-1-1 and B-1-33 instead of Aniline were used. Got MS: [M + H] ⁺ = 1001

Manufacturing example  1-1-10. Preparation of Formula 1-2-10

[Formula A-2-1] [Formula 1-2-10]

In the preparation example of Chemical Formula 1-2-1, it was reacted in the same manner as Chemical Formula 1-2-10, except that A-2-1 instead of Formula A-1-1 and B-1-34 instead of Aniline were used. Got MS: [M + H] ⁺ = 961

Manufacturing example  1-1-11. Preparation of Formula 1-2-11

[Formula A-2-1] [Formula 1-2-11]

In the preparation example of Chemical Formula 1-2-1, it was reacted in the same manner as Chemical Formula 1-2-11 except that A-2-1 instead of Formula A-1-1 and B-1-35 instead of Aniline were used. Got MS: [M + H] ⁺ = 911

Manufacturing example  1-1-12. Preparation of Formula 1-2-12

[Formula A-2-1] [Formula 1-2-12]

In the preparation example of Chemical Formula 1-2-1, Chemical Formula 1-2-12 was reacted in the same manner, except that Chemical Formula A-1- was used instead of A-2-1-1 and Chemical Formula B-1-36 was used instead of Aniline. Got MS: [M + H] ⁺ = 909

Manufacturing example  1-1-13. Preparation of Formula 1-2-13

[Formula A-2-1] [Formula 1-2-13]

In the preparation example of Chemical Formula 1-2-1, it was reacted in the same manner as Chemical Formula 1-2-13, except that A-2-1 instead of Formula A-1-1 and B-1-7 instead of Aniline were used. Got MS: [M + H] ⁺ = 809

5 is a diagram showing NMR data of Chemical Formulas 1-2-13.

Add Manufacturing example .

The compounds of Formula 1 herein are the following Formulas A-1-1 to A-10-1 and B-1-1 to B-1-36, B-2-1 to B-2-5 and B-3-1 It is prepared by reacting with any one of B-3-3.

[Formula A-1-1] [Formula A-2-1]

[Formula A-3-1] [Formula A-4-1]

[Formula A-5-1] [Formula A-6-1]

[Formula A-7-1] [Formula A-8-1]

[Formula A-9-1] [Formula A-10-1]

[Formula B-1-1] [Formula B-1-2] [Formula B-1-3]

[Formula B-1-4] [Formula B-1-5] [Formula B-1-6]

[Formula B-1-7] [Formula B-1-8] [Formula B-1-9]

[Formula B-1-10] [Formula B-1-11] [Formula B-1-12]

[Formula B-1-13] [Formula B-1-14] [Formula B-1-15]

[Formula B-1-16] [Formula B-1-17] [Formula B-1-18]

[Formula B-1-19] [Formula B-1-20] [Formula B-1-21]

[Formula B-1-22] [Formula B-1-23] [Formula B-1-24]

[Formula B-1-25] [Formula B-1-26] [Formula B-1-27]

[Formula B-1-28] [Formula B-1-29] [Formula B-1-30]

[Formula B-1-31] [Formula B-1-32] [Formula B-1-33]

[Formula B-1-34] [Formula B-1-35] [Formula B-1-36]

[Formula B-2-1] [Formula B-2-2] [Formula B-2-3]

[Formula B-2-4] [Formula B-2-5]

[Formula B-3-1] [Formula B-3-2] [Formula B-3-3]

< Example >

Example  One.

[Formula A]

Chlorobenzene (1.4 ml) was added dropwise to the material of Formula A (12.5 mg) under a nitrogen atmosphere and stirred at room temperature to prepare an ink. After the prepared ink was applied onto the cleaned ITO glass substrate, it was fired at 200 ° C. for 1 hour under nitrogen to obtain a uniform thin film. This was introduced into a vacuum deposition apparatus, and NPB, DPBVi, Bphem, LiF, and Al were sequentially set to 20 nm, 50 nm, 20 nm, 30 nm, 0.5 nm, and 100 nm, respectively, and then deposited under pressure of 1ⅹ10 ^-7 Torr or less. Was done. The deposition rate of LiF is 0.01-0.05 nm / s, and the layer excluding LiF is 0.1-0.5 nm / s.

Example  2.

[Formula B]

A device was manufactured in the same manner as in Example 1, except that chlorobenzene (1.4 ml) was added dropwise to the material of Formula B (12.5 mg) under a nitrogen atmosphere and stirred at room temperature to prepare an ink.

Example  3.

[Chemical Formula C]

A device was manufactured in the same manner as in Example 1, except that chlorobenzene (1.4 ml) was added to the material of Formula C (12.5 mg) under a nitrogen atmosphere and stirred at room temperature to prepare an ink.

< Comparative example >

Comparative example  One.

The polymer (12.5 mg, Mw = 22,000 g / mol) was added dropwise to chlorobenzene (1.4 ml) under a nitrogen atmosphere and stirred at room temperature to prepare an element in the same manner as in Example 1, except that ink was prepared.

The experimental results for the organic light emitting device manufactured in Examples 1 to 3 and Comparative Example 1 are shown in FIGS. 2 to 4.

2 is a view showing a driving voltage according to the current density. It can be seen from FIG. 2 that the driving voltages of Examples 1 to 3 are the same at low current densities and thus the efficiency is excellent.

3 is a diagram showing power efficiency according to current density. It can be seen from FIG. 3 that the power efficiency of Examples 1 to 3 is excellent.

4 is a diagram showing a luminance value (%) over time. It can be seen from FIG. 4 that Examples 1 to 3 have excellent luminance values over time compared to Comparative Example 1.

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

Claims (13)

Fluorene derivatives represented by the following formula 2 or formula 3:
[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,
L1 to L3 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; A substituted or unsubstituted cycloalkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted ester group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ar1 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; A fluorenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; Or a substituted or unsubstituted heteroaryl group,
Ar2 and Ar3 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; A fluorenyl group unsubstituted or substituted with an alkyl group, an arylamine group, or a heteroaryl group; Or a substituted or unsubstituted heteroaryl group,
L4 is a phenylene group, biphenylene group, terphenylene group, naphthylene group or fluorenylene group,
X1 and X2 are the same as or different from each other, and each independently a thermosetting group; Or a photocurable group,
n1 is an integer from 0 to 4,
n2 is an integer from 0 to 3,
When n1 and n2 are each 2 or more, the substituents in parentheses are the same as or different from each other. delete delete The method according to claim 1, wherein the thermosetting group and photocurable group is a fluorene derivative of any one of the following structures:

In the above structure,
R4 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
A1 to A3 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. delete Coating composition comprising a fluorene derivative according to claim 1 or 4. The coating composition of claim 6, wherein the coating composition further comprises a p-doped material. The coating composition according to claim 7, wherein the p-doped material is represented by any one of the following Chemical Formulas 2-1 to 4-1.
[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

The method according to claim 6, The coating composition is a single molecule comprising a thermosetting group or a photocurable group; Or a coating composition further comprising a single molecule containing a terminal group capable of forming a polymer by heat. Cathode;
Anode; And
It includes at least one organic layer provided between the cathode and the anode,
At least one layer of the organic material layer includes a cured product of the coating composition of claim 6,
The cured product of the coating composition is an organic light emitting device in which the coating composition is cured by heat treatment or light treatment. The organic light emitting device of claim 10, wherein the organic material layer containing the cured product of the coating composition is a hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection. 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 includes forming one or more organic material layers using the coating composition of claim 6. The method according to claim 12, Forming an organic material layer formed using the coating composition is
Coating the coating composition on the cathode or anode; And
A method of manufacturing an organic light emitting device comprising the step of heat-treating or photo-treating the coated coating composition.

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