WO2018190522A1

WO2018190522A1 - Novel compound and organic light emitting device comprising same

Info

Publication number: WO2018190522A1
Application number: PCT/KR2018/002941
Authority: WO
Inventors: 양정훈; 이동훈; 허정오; 장분재; 강민영; 허동욱; 한미연; 정민우
Original assignee: 주식회사 엘지화학
Priority date: 2017-04-12
Filing date: 2018-03-13
Publication date: 2018-10-18

Abstract

The present invention provides a novel compound and an organic light emitting device comprising the same, the novel compound including a substituted or unsubstituted biphenyl fluorenyl group as a core structure, wherein any one benzene ring in the fluorenyl group has two functional groups of different structures bound thereto.

Description

[Name of invention]

Novel compound and organic light emitting device comprising the same

Technical Field

This application is subject to Korean Patent Application No. 10—2017-0047544, issued April 12, 2017 and

2018 _. Claiming the benefit of priority based on Korean Patent Application No. 10-2018-0027124 dated March 7th. All contents disclosed in the literature of the corresponding Korean patent applications are included as part of this specification.

The present invention relates to a novel compound and an organic light emitting device comprising the same.

[Technique to become background of invention]

Generally organic luminescence. Phenomenon refers to a phenomenon that converts electrical energy into light energy using organic materials. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent researches have been conducted because of excellent luminance ᅳ driving voltage and response speed characteristics.

The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. The organic layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer. Hole transport layer, light emitting layer. It may be made of an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. It will glow when the excitons fall back to the ground. Development of new materials for organic materials used in organic light emitting devices as described above _. It is being demanded continuously.

[Content of invention]

Problem to be solved

SUMMARY OF THE INVENTION An object of the present invention is a novel compound capable of improving efficiency and low driving voltage and lifetime and characteristics when used as a material of an organic layer of an organic light emitting device, and An organic light emitting device is provided.

[Measures of problem]

The present invention provides a compound of formula

In Formula 1 above.

A is C6-C20 aryl unsubstituted or substituted with a cyano group or a diphenylphosphine oxide group; Fluorenyl unsubstituted or substituted with a cyano group; And it is selected from the group consisting of heteroaryl containing 2 to 9 carbon atoms containing at least one nitrogen atom (N)

Ar ₂ is selected from the group consisting of functional groups of Formulas 2a to 2e.

2a] ᅳ

b]

[Formula 2c]

In Chemical Formulas 2a to 2e.

Ar ₃ to Ar ₅ are each independently hydrogen; heavy hydrogen; Alkyl having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Or C2-C20 heteroaryl including one or more heteroatoms selected from the group consisting of 0, N, Si, and S; and ᅳ and L ₂ are each independently a bond; Or substituted or unsubstituted phenylene

Ri and ¾ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted alkyl having 1 to 60 carbon atoms; Substituted or unsubstituted haloalkyl having 1 to 60 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 60 carbon atoms; Substituted or unsubstituted haloalkoxy having 1 to 60 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 60 carbon atoms; Substituted or unsubstituted aryl having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 60 carbon atoms; Or substituted or unsubstituted 0, N. Heteroaryl having 2 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of Si and S,

a and b are each independently an integer of 0 to 3, and c is an integer of 0 or 1. Also. The present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of Formula 1.

【Effects of the Invention】

The compound of formula 1 described above can be used as the material of the organic layer of the organic light emitting device. In the organic light emitting device, efficiency, low driving voltage, and / or lifetime characteristics can be improved. Especially. The compound represented by Chemical Formula 1 may be used as a light emitting, electron transport, or electron injection material.

[Brief Description of Drawings]

1 shows a substrate 1, an anode 2, and a light emitting layer 3. The example of the organic light emitting element which consists of the cathode 4 is shown.

2 is a substrate (1). An anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer (7). The example of the organic light emitting element which consists of the electron carrying layer 8 and the cathode 4 is shown. [Specific contents to carry out invention]

Below. It will be described in more detail to help the understanding of the present invention.

In the present specification, ᅳ means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; ^"An aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl group; boron group; Alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Haloalkyl; Haloalkoxy; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group including one or more hetero atoms selected from the group consisting of 0, N, Si, and S. It means that the substituted or unsubstituted two or more substituents of the substituents exemplified above. For example, "the substituent to which two or more substituents are linked" may be a biphenyl group. In other words. The biphenyl group may be an aryl group. It can be interpreted as a substituent in which two phenyl groups are linked.

Carbon number of the carbonyl group in the present specification is not particularly limited, but carbon number 1 It is preferable that it is 40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the hydrogen of the carboxyl group may be substituted with a linear, 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 carbon number of the imide group is not particularly limited. It is preferable that it is C1-C25. Specifically, the compound may be of the structure

In this specification. The silyl group is specifically trimethylsilyl group. Triethylsilyl group. t-butyldimethylsilyl group. Vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group. Diphenylsilyl group and phenylsilyl group and the like, but is not limited thereto. In this specification. The boron group is specifically trimethylboron group. Triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group and the like, but is not limited thereto. In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In this specification. The alkyl group may be straight or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include. Methyl, ethyl, propyl, n-propyl, isopropyl. Butyl, n-butyl, isobutyl, t-ert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl. Isopentyl, neopentyl, ter t—pentyl. Nuclear chamber, n-nuclear chamber, 1-methylpentyl, 2-methylpentyl. 4-methyl-2-pentyl ᅳ 3, 3-dimethylbutyl. 2-ethylbutyl, heptyl, n-heptyl, 1-methylnucleosilcyclocyclopentylmethyl. Octyl ᅳ n—octyl, ter t-octyl, 1—methylheptyl, 2-ethylnucleus, 2—propylpentyl, n-nonyl. 2. 2—Dimethylheptyl, 1-ethyl-propyl. 1, 1-dimethyl-propyl, isonuclear chamber, 2-methylpentyl. 4— methyl nucleus, 5-methyl nucleus, etc. It is not limited to these.

In this specification. The alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment. Carbon number of the said alkenyl group is 2-20. According to another embodiment. Carbon number of the said alkenyl group is 2-10. According to another exemplary embodiment, the carbon number of the alkenyl group is. 2 to 6. Specific examples include vinyl, 1-propenyl. Isopropenyl, 1-butenyl. 2—butenyl, 3 one butenyl, 1 one 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, stilbenyl, styrenyl, and the like, but are not limited to these.

In this specification. The cycloalkyl group is not particularly limited. Carbon number

Preferably from 3 to 60; According to one embodiment. Carbon number of the said cycloalkyl group is 3-30. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment. , The cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl. Cyclobutyl, cyclopentyl, 3-methylcyclopentyl. 2.3-dimethylcyclopentyl, cyclonuclear chamber, 3- Methylcyclonuclear chamber. 4-methylcyclonuclear chamber, 2, 3-dimethylcyclonuclear chamber, 3,4,5-trimethylcyclonuclear chamber, 4-tert-butylcyclonuclear chamber. 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. It may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as the monocyclic aryl group, but is not limited thereto. As said polycyclic aryl group, a naphthyl group, anthracenyl group, a phenanthryl group, a pyrenyl group, a perrylenyl group, a krasenyl group. Fluorenyl group and the like. It is not limited to this.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. The fluorenyl group is substituted

Can be. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heteroaryl or heterocycloalkyl group containing one or more heteroatoms selected from the group consisting of 0, N, Si, and S as heterologous elements. Although carbon number is not specifically limited, It is preferable that it is C2-C60. Examples of the heterocyclic group include thiophene group and furan group. Pyrrole. Imidazole group, thiazole group. Oxazole group oxadiazole group. Triazole. Pyridyl groups. Bipyridyl groups, pyrimidyl groups, triazine groups, acridil groups. Pyridazine. Pyrazinyl groups. Quinolinyl group, quinazolin group, quinoxalinyl group. Phthalazinyl group. Pyridopyrimidinyl groups. Pyridopyrazinyl groups. Pyrazino pyrazinyl, isoquinoline, indole. Carbazole group, benzoxazole group, benzoimidazole group. Benzothiazole group. Benzocarbazole group. Benzothiophene group. Dibenzothiophene group, benzofuranyl group, phenanthroline group. Isoxazolyl group Thiadiazolyl group, phenothiazinyl group, dibenzofuranyl group and the like, but are not limited thereto.

In this specification. The aryl group in an aralkyl group, an aralkenyl group, an alkylaryl group, and an arylamine group is the same as the example of the aryl group mentioned above. In this specification. The alkyl group in the aralkyl group, alkylaryl group, and alkylamine group is the same as the example of the alkyl group mentioned above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, except that the arylene is a divalent group, the description about the aryl group described above may be applied. In the present specification, except that the heteroarylene is a divalent group, the description of the aforementioned heterocyclic group may be applied. In this specification. The hydrocarbon ring is not monovalent. The above description about the aryl group or cycloalkyl group can be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic ring is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding. On the other hand, the present invention provides a compound of formula

In Chemical Formula 1,

Aryl having 6 to 20 carbon atoms substituted or unsubstituted with a cyano group or a diphenylphosphine oxide group; Fluorenyl unsubstituted or substituted with a cyano group; And it is selected from the group consisting of heteroaryl containing 2 to 9 carbon atoms containing at least one N,

[Formula 2a]

In Chemical Formulas 2a to 2e.

Ar ₃ to Ar ₅ represent ^hydrogen, each independently selected; Distillate; C1-C20; C6-C20 aryl; Or heteroaryl having 2 to 20 carbon atoms containing at least one hetero atom from the group consisting of 0, N, Si and S.

L _! And L ₂ are each independently bonded; Or substituted or unsubstituted phenylene, Ri and R ₂ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted alkyl having 1 to 60 carbon atoms; Substituted or unsubstituted haloalkyl having 1 to 60 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 60 carbon atoms; Substituted or unsubstituted haloalkoxy having 1 to 60 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 60 carbon atoms; Substituted or unsubstituted aryl having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of 0, N, Si and S.

a and b are each independently an integer of 0 to 3, and c is an integer of 0 or 1.

Specifically, the compound of Formula 1 includes a substituted or unsubstituted biphenyl fluorenyl group as a central structure, and the functional groups of A and Ar ₂ for each of the benzene ring moieties in the fluorenyl group are each L and Having an asymmetrical structure bonded through ₂ , and having an symmetrical structure in which the same functional groups are bonded around the biphenylfluorenyl group, the electron transport ability through various combinations. Bandgap, energy level and thermal characteristics can be adjusted more easily.

More specifically, the compound of Formula 1 may be one having a structure of any one of the following formula la to lc:

In the above formula la to lc,

Xi and ¾ are either -LrA and — L ₂ — Ar ₂ . They are not identical to each other,

Ri, R ₂ , Li, L ₂ . An. Ar ₂ , a and b are as defined above.

In general, the solubility and thermal properties of the compounds depend on the crystallinity of the molecules, when the more structural obstacles are large, the crystallinity of the molecules is lowered, the process solubility and thermal properties. Is improved. therefore. According to an exemplary embodiment of the present specification,-Li-Ar, and — Compound represented by the formula (1) where —L ₂ —Ar ₂ is substituted in a structurally hindered position, —L 厂 A and ᅳ L ₂ -Ar ₂ is structural As compared to the compound substituted two at the position with few obstacles, the process solubility and thermal properties of the molecule is improved, thereby. Compound represented by the formula (1) has a process advantage in the synthesis, and when used in an organic light emitting device, there is an advantage that the thermal properties are improved.

Also. As in the structures of formula la-lc above: two functional groups bonded to a biphenylfluorenyl group. When the positions of-and An and -L ₂ -Ar ₂ are asymmetrically specified, the distance between-and -L ₂ of the conjugate length is shorter than that of the symmetrical molecule, so that the electron and hole transport ability can be more effectively controlled. .

In Formula 1 above. A is more specifically, phenyl, naphthalenyl ᅳ anthracenyl substituted or unsubstituted with a cyano group or a diphenylphosphine oxide group. Phenanthrenil. Fluorenyl. Pyridinyl, pyridazinyl, pyrimidinyl, triazinyl, benzopyridinyl, benzopyridazinyl. It may be selected from the group consisting of benzopyrimidinyl and benzopyridanyl, and more specifically may be selected from the group consisting of the following functional groups:

In the above structural formulas, in and n are each independently an integer of 0 or 1.

In Formula 1, Ar ₂ may be any one of the functional groups of Formulas 2a to 2e, and in Formulas 2a to 2e. Ar ₃ to Ar ₅ is more specifically. Each may independently be selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms, and phenyl, and more specifically, may be selected from the group consisting of hydrogen, methyl and fe.yl.

In Formula 1, a linking group and ^' L ₂ are each independently a bond; Or substituted or unsubstituted phenylene, and in the case of substituted phenylene, At least one hydrogen in phenylene is deuterium; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted alkyl having 1 to 60 carbon atoms; Substituted or unsubstituted haloalkyl having 1 to 60 carbon atoms; Substituted or unsubstituted C1-C60 alkoxy; Substituted or unsubstituted haloalkoxy having 1 to 60 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 60 carbon atoms; Substituted or unsubstituted aryl having 6 to 60 carbon atoms; Substituted or unsubstituted 6 to 6 carbon atoms

Aryloxy of 60; Or substituted or unsubstituted, which may be substituted with a heteroaryl having 2 to 60 carbon atoms containing at least one hetero atom selected from the group consisting of 0, N, Si and S.

More specifically, and L ₂ are each independently a bond; Or unsubstituted phenylene.

If L and L ₂ are functional groups having a large size such as anthracene, there is a fear of a decrease in color purity due to light emission of the functional group skeleton itself.

On the other hand, in the compound of Formula 1 according to an embodiment of the present invention, two functional groups — — An and —L ₂ —Ar ₂ bonded to a biphenylfluorenyl group may have different structures.

Specifically with two functional groups and -L ₂ -Ar ₂ . And L ₂ may be different, or A and Ar ₂ may be different. Or and L ₂ . And

Ar ^ Ar _{2 may} both have different structures. More specifically, Ar ₂ and Ar ₂ may have different structures. When the two functional groups bonded to the biphenyl fluorenyl group in this way have a different structure. Compared to the case of having the same structure, the electron transport ability. The bandgap energy level and thermal characteristics can be adjusted more easily.

In addition. The above formula. In 1. Two phenyl groups bonded to a fluorenyl group may each be substituted one or more with a substituent and R _2, where: And ¾ are as defined above. More specifically and R ₂ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Alkyl having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms. More specifically, Ri and ¾ are each independently. Hydrogen. heavy hydrogen. Halogen, cyano. Nitro, methyl. Or phenyl. In addition. The number of substitutions (a and b) of or ¾ for each phenyl group is each independently 0 to , More specifically, 0 or 1.

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The compound of Formula 1 includes a substituted or unsubstituted biphenyl fluorenyl group as a central structure, and the functional groups of An and Ar ₂ for each of the benzene ring portions in the fluorenyl group are each represented by L ₂ and L ₂ . It has an asymmetric structure containing two functional groups bonded together. Furthermore, at least one of the two functional groups includes at least one functional group of a heterocyclic group containing a nitrogen atom, thereby active electron transport capacity. Bandgap. Energy level. It can show the effect of controlling thermal characteristics. Therefore, the organic light emitting device using the same has the same functional groups bonded to the benzene ring portions present on both sides of the fluorenyl group, and the biphenyl fluorenyl group is mainly used. High efficiency compared to organic light-emitting device employing a compound having a symmetrical structure. It may have a low driving voltage, high brightness and long life.

On the other hand, the compound of Formula 1 is. It can be prepared by the same method as in Banung Formula 1.

In Reaction Formula 1, X is a halogen group such as chloro or boromo.

Y is boronic acid. Boronic acid ester. Or a boron (B) -containing organic group such as boronic acid pinacol ester group. R ₂ , L ₂ . An, Ar ₂ . a and b are as defined above.

In the reaction formula 1, organoboron compound (II) is

Organoboron compound (II) comprises a functional group of -L ₂ -Ar ₂ , while halide (III) comprises a functional group, and halide (III) is illustrated as including a functional group of -L ₂ -Ar ₂ It may also contain a functional group of -LrA.

Specifically, the compound (I) of Formula 1 may be prepared by reacting the organoboron compound (II) with Suzuki coupling in the presence of the halide (III), a base and a palladium catalyst.

The base may be sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide, and the like, and the palladium catalyst may be tetrakis- (triphenylphosphine) palmulum (Pcl (PPH ₃ ) ₄ ), paramalacetate, or the like. This can be used. In addition, the reaction may be carried out in an organic solvent such as tetrahydrofuran (THF), NN-dimethylformamide (DMF), dimethyl sulfoxide (DMS0) or toluene. In addition. The Suzuki coupling reaction of the reaction formula 1 may be performed in the range of 80 ^° C. to 120 ^° C.

On the other hand, the organoboron compound (II) may be prepared directly, or commercially It can also be obtained.

The organoboron compound (Π) may be determined in kind depending on the positions of Li—Ar and L ₂ —Ar ₂ functional groups bonded to the biphenylfluorenyl group in the compound of Formula 1 to be finally prepared. For example, the compounds of the formulas la to lc of the present invention may be prepared using the organoboron compounds prepared in the same manner as in the schemes 2 to 4, respectively. Reaction Schemes 2 to 4 are only examples for describing the present invention, but the present invention is not limited thereto.

[Banungsik 3]

In Schemes 2 to 4, LL L ₂ . An and Ar ₂ are as previously defined, NBS is 11—bromosuccininiide, DMF is dimethyl Formamide (Dimethyl Formami de), THF is tetrahydrofuran. AN is acetonitrile, and KOAc is potassium acetate.

The compound of Formula 1 may be prepared by appropriately replacing the starting material in accordance with the structure of the compound to be prepared with reference to the reaction formula 1 to 4.

. On the other hand, the present invention provides an organic light emitting device comprising the compound of Formula 1. In one embodiment, the present invention comprises a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Chemical Formula 1. do.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. for example. The organic light emitting device of the present invention is a hole injection layer, a hole transport layer as an organic material layer. Light emitting layer. It may have a structure including an electron transport layer, an electron injection layer and the like. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

Also. The organic ^layer, a hole injection dancing. Hole transport layer. Or a layer for simultaneously injecting and transporting holes, wherein the hole injection layer. Hole transport layer. Alternatively, the layer for simultaneously injecting and transporting a hole may include a compound represented by Chemical Formula 1.

In addition, the organic layer may include a light emitting layer. The light-emitting layer ^is, comprising a compound of the formula (1).

Also. The organic layer is an electron transport layer. Or an electron injection layer. The electron transport layer, or the electron injection insect comprises a compound represented by the formula (1).

Also. The electron transport layer. The electron injection layer or the layer for electron injection and electron transport to the verb includes the compound represented by Chemical Formula 1. Especially. The compound represented by Formula 1 according to the present invention has excellent thermal stability, high triplet energy (ET), and hole stability. In addition, when the compound represented by Chemical Formula 1 is used in an organic material layer capable of simultaneously injecting and transporting electrons, an n-type dopant used in the art may be mixed and used. Also. The organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Chemical Formula 1.

Also. An organic light emitting device according to the present invention. The organic light emitting device may have a structure in which one or more organic material layers and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. for example. The structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

1 shows a substrate 1, an anode 2. The example of the organic light emitting element which consists of the light emitting layer 3 and the cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

2 shows a substrate 1. Anode (2). Hole injection layer (5). Hole transport layer (6), light emitting layer (7). The example of the organic light emitting element which consists of the electron carrying layer 8 and the cathode 4 is shown. In such a structure, the compound represented by Formula 1 is the hole injection layer, a hole transport layer. It may be included in one or more layers of the light emitting layer and the electron transport layer.

An organic light emitting device according to the present invention. One or more layers of the organic material layer may be prepared by materials and methods known in the art, except that the compound represented by Chemical Formula 1 is included. Also. 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.

for example. An organic light emitting device according to the present invention is a first electrode on a substrate. The organic material layer and the second electrode may be sequentially stacked. At this time. By using a physical vapor deposition method (PVD) such as sputtering or e-beam evaporat km. A metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and then used as a cathode thereon. It can be prepared by depositing a material that can be. In addition to methods like this. The organic material layer from the negative electrode material on the substrate. An anode material may be sequentially deposited to make an organic light emitting device.

In addition, the compound represented by Formula 1 may be used to prepare an organic light emitting device. The organic layer may be formed by a solution coating method as well as a vacuum deposition method. here . Solution coating refers to spin coating. Dip coating. Doctor Blading. Inkjet printing. Screen printing. The spray method means coating, but is not limited to these. ᅳ

In addition to methods like this. The organic layer from the negative electrode material on the substrate. An organic light emitting device may be manufactured by sequentially depositing an anode material (W0 2003/012890). However, the manufacturing method is not limited thereto.

As an example. The first electrode is an anode. The second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include vanadium, chromium and copper. Metals such as zinc or gold or alloys thereof; Zinc oxide. Indium oxide. Indium tin oxide (ΠΌ). Metal oxides such as zinc oxide (IZ0); ΖηΟ: Α1 or SN0 ₂ : A combination of a metal and an oxide such as Sb; Poly (3-methylthiophene). Conductive polymers such as poly [3.4- (ethylene-1, 2-dioxy) thiophene] (PED0T), polypyrrole and polyaniline. It is not limited only to these.

It is preferable that the anode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material are magnetite. calcium. Sodium ^. . Kalm. Titanium, indium, yttrium. lithium. gadolinium. Aluminum, silver. Metals such as tin and lead or alloys thereof; multimodal structural materials such as LiF / Al or Li0 ₂ / Al. It is not limited only to these. The hole injection material may be a charge for injecting holes from an electrode. As the hole injection material, it has the ability to transport holes. It has an excellent hole injection effect on the light emitting layer or the light emitting material, and prevents the excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material. Also. Compounds excellent in thin film formation ability are preferred. It is preferable that the HOMCX highest occupied molecul ar orbi ta) of the hole injection material is between the work function of the anode material and H0M0 of the surrounding organic layer. Specific examples of the hole injection material include metal porphyr (porphyr in), oligothiophene, arylamine-based organic matter, nucleonitrile nucleated azatriphenylene-based organic material. Quinacridone (qui nacr i done) Organics. Of perylene series Organic materials, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer for receiving holes from the hole injection layer to transport holes to the light emitting layer. As a material for transporting holes from the anode or the hole injection layer to the hole transporting material, a material having high mobility to holes is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Ak _l3 ); Carbazole series compounds; Diiiier i zed styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Polymers of the poly (P-phenylenevinylene) (PPV) family; Spi ro compounds; Polyfluorene. Rubren, etc. It is not limited only to these.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic compounds include carbazole derivatives and dibenzofuran derivatives. Ladder type furan compounds, pyrimidine derivatives, and the like. It is not limited to this.

Dopant materials include aromatic amine derivatives. Strylamine compound, boron complex, fluoranthene compound. Metal complexes; Specifically, as an aromatic amine derivative, as a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, pyrene having an arylamino group. Anthracene, chrysene. Periplanten. The styrylamine compound is a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine. Aryl group. Substituents selected from one or two or more selected from the group consisting of silyl, alkyl, cycloalkyl and arylamino groups are substituted or unsubstituted. Specifically styrylamine ， styryldiamine ᅳ Styryltriamine. Styryltetraamine and the like, but is not limited thereto. In addition, as a metal complex, an iridium complex. There is a platinum complex. It is not limited to this. The dopant content may be from 1% to 99% relative to the host amount of the light emitting layer. The electron transporting material in the electron in layer receives an electron from the injection layer of transporting electrons to the electron transport material balgwangchung receives electrons from the cathode as a material that can move to the light-emitting ^"layer. Materials with high mobility for the electron are suitable. Specific examples include Al complexes of 8—hydroxyquinoline; Complexes including A1; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. 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 conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer for injecting electrons from the electrode. Has the ability to transport electrons, the effect of electron injection from the cathode. It has an excellent electron injection effect with respect to a light emitting layer or a light emitting material, and prevents the movement of the excitons produced | generated in the light emitting layer to the hole injection layer, and also. Compounds excellent in thin film formation ability are preferred. Specifically, fluorenone and anthraceno dimethane. Diphenoquinone, thiopyran dioxide oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal complex compounds and nitrogen-containing five-membered ring derivatives, It is not limited to this. Examples of the metal complex compound include 8-hydroxyquinolinato lithium lithium bis (8-hydroxytunolinato) zinc and 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) chlorogalm, bis (2-methyl-8-quinolinato) (0-cresolato) gallium , Bis (2—methyl-8—quinolinato) (1—naphtho) aluminum,. Bis (2-methyl-8-quinolinato) (2-naphlato) gallium and the like. It is not limited to this. The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

Also. The compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The production of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Compound A (20.00g, in 500ml equipotential bottom flask in nitrogen atmosphere

32.12 隱₀ 1). 2-bromonaphthalene (6.61 g, 32.12 μl) was completely dissolved in 300 ml of tetrahydrofuran (THF), followed by addition of 2M aqueous potassium carbonate solution (150 ml), followed by tetrakis- (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ) (l.llg. 0.96 隱 01) was added thereto, followed by heating and stirring for 3 hours. Lower the temperature to room temperature (23 ± 5 ^° C) and scrub the water layer. After drying over anhydrous magnesium sulfate and concentrated under reduced pressure ᅳ recrystallized with 180ml ethyl acetate to give Compound 1 (11.9g, 59%) ol.

MS [M + H] ⁺ = 622

Compound in 500ml isometric bottom flask in atmosphere 28.91 mmol). After 2-bromopyridine (4.57g, 28.91 謹 101) was completely dissolved in 300nil of tetrahydrofuran. 2M aqueous potassium carbonate solution (150 ml) was added, and After adding tetrakis- (triphenylphosphine) palladium (l.OOg, 0.8 groups 誦₀ 1). Heat stirring for 3 hours. Lower the temperature to room temperature (23 ± 5 ^° C) and remove the water layer. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure and recrystallized with 180 ml of etalacetate to prepare Compound 2 (8.79 g. 55%).

MS [M + H] ⁺ = 573

After dissolving Compound C (22.90 g. 38.3½ niol) and 6-bromoquinoline (7.97 g, 38.34 μl) in 300 nil of tetrahydrofuran in a 500 ml back bottom flask in a nitrogen atmosphere _. 2M aqueous potassium carbonate solution (150 ml) was added. Tetrakis- (triphenylphosphine) palladium (1.32 g, 1.15 nimol) was added thereto, followed by heating and stirring for 3 hours. Lower the temperature to room temperature (23 ± 5 ^° C) and remove the water layer. The mixture was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 180 ml of ethyl acetate to obtain compound 3 (16.5 g. 63%).

MS [M + H] ⁺ = 598 <Preparation Example 4>

In 500ml deunggeun bottom flask under nitrogen compound D (19.80g. 29.30mmol), 7一-bromo-quinoline, 2M potassium carbonate aqueous solution (15 () was completely dissolved (6.09g. 29.3丽₀ 1) in tetrahydrofuran 300ml ml) was added and tetrakis- (triphenylphosphine) pall (l.Olg. 0.88 mmol) was added, followed by heating and stirring for 3 hours. Lower the temperature to room temperature (23 ± 5 ^° C) and remove the water layer. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure and recrystallized with 180 ml of ethyl acetate to obtain Compound 4 (12.3 g, 62%). ^'

MS [M + H] ⁺ = 676

Formula 5 was prepared in the same manner as in Preparation Example 1, except that 3- (4—bromophenyl) pyridine was used instead of 2-bromonaphthalene in Preparation Example 1.

MS [M + H] + = 648 - ' jje versed 6>

. Formula 6 was prepared in the same manner as in Preparation Example 1, except that 4-bromobenzene was used instead of 2-bromonaphthalene in Preparation Example 1.

MS [M + H] + = 572

Preparation Example 1 2-bromonaphthalene instead of 4-bromo-1. Formula 1 was prepared in the same manner as in Preparation Example 1, except that 1′-biphenyl was used. ᅳ

MS [M + H] + = 572

[A]

In Preparation Example 1, 4-bromobenzonitrile was used instead of 2—bromonaphthalene. Except that. Formula Compound 8 was prepared in the same manner as in Preparation Example 1.

MS [M + H] + = 597

Except for using 4-bromobenzene instead of 6—bromoquinoline in Preparation Example 3. Compound 9 of the above structure was prepared in the same manner as in Preparation Example 3. -

MS [M + H] ⁺ = 547

Compound 10 of the above structure was prepared in the same manner as in Preparation Example 3, except that 4-bromo-1.1′-biphenyl was used instead of 6-bromoquinoline in Preparation Example 3.

MS [M + H] + = 623 Example 11

Compound 11 of the above structure was prepared in the same manner as in Preparation Example 3, except that 4'-bromo biphenyl] -4-carbonitrile was used instead of 6-bromoquinoline in Preparation Example 3.

MS [M + H] + = 648

Except that was prepared in the same manner as in Preparation Example 3 Compound 12 of the above structure was prepared.

MS [M + H] + = 597

Compound 13 of the above structure was prepared in the same manner as in Preparation Example 3, except that 2-bromonaphthalene was used instead of 6-bromoquinoline in Preparation Example 3.

MS [M + H] + = 597. .

[D] [14]

In Preparation Example 4 Compound 14 of the above structure was prepared in the same manner as in Preparation Example 4, except that 4-bromobenzene was used instead of 7—bromoquinoline.

4-Bromo-1 instead of 7-bromoquinoline in Preparation Example 4. Except for using the Γ -biphenyl, the compound 15 of the above structure was prepared in the same manner as in Preparation Example 4.

MS [M + H] + = 625

Preparation 16 _, except that 2-bromonaphthalene instead of 7-bromoquinoline in 4, was carried out in the same manner as in Preparation Example 4 to prepare a compound of the structure 16.

MS [M + H] + = 676

Compound 17 of the above structure was prepared in the same manner as in Preparation Example 4, except that 4′-bromo biphenyl] -4-carbonitrile was used instead of 7—bromoquinoline in Preparation Example 4.

MS [M + H] + = 727 C. Example 18>

Compound F (19.80g. 29.30mmol) in 500nil equipotential bottom flask in nitrogen atmosphere. 2— (4.4,5,5—tetramethyl-1,3,2-dioxabororen-2-yl) -1,10-phenanthroline (8.83 g, 28.86 mmol) is completely dissolved in 300 nil of tetrahydrofuran ᅳ 2M aqueous potassium carbonate solution (150 ml) was added, tetrakis- (triphenylphosphine) palm (lg, 0.87x01) was added, and the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature (23 ± 5 ^° C.), the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 180 ml of ethyl acetate to prepare compound 18 (10.5 g. 64%).

MS [M + H] ⁺ = 572

Manufacture example 19>

[F] [19]

In Preparation Example 18 2 ′ (4, 4, 5, 5-tetramethyl-1,3, 2-dioxabororen-2—yl)-1, 2-phenyl instead of 10-phenanthrene- 9- (4 , 4, 5, 5—Tetramethyl-1, 3, 2—dioxaborene-2 days) -1.10—Phenanthrene was used in the same manner as in Preparation Example 18 except that Compound 19 was prepared.

MS [M + H] ⁺ = 649

[G]

Compound G (20.00 g. 33.50 mmol) in a 500 ml equipotential bottom flask in a nitrogen atmosphere. After completely dissolved in 300 ml of bromo benzene (5.26 g, 33.50 inmoOol tetrahydrofuran), 2 M aqueous potassium carbonate solution (150 ml) was added, followed by tetrakis- (triphenylphosphine) palladium (1.16 g, 1.00 μ ol). The mixture was heated and stirred for 3 hours, and then cooled to room temperature (23 ± 5 ^° C.), the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with ethyl acetate 18 (12. lg, 66%) was prepared.

MS [M + H] + = 547

Compound H (20.00 g. In 500 ml equipotential bottom flask in nitrogen atmosphere.

33.50nimol), 2— (2—bromophenyl) pyridine (7.84g, 33.5 () 隱 01) was added to tetrahydrofuran

After complete dissolution in 300ml, 2M _. An aqueous potassium carbonate solution (150 ml) is added and tetrakis-

(Triphenylphosphine) palladium (1.16 g, 1.00 Pa ol) was added thereto, followed by heating and stirring for 3 hours. Lower the temperature to room temperature (23 ± 5 ^° C), remove the water layer, anhydrous After drying over magnesium sulfate and concentrated under reduced pressure. Ethyl acetate

Recrystallization gave compound 21 (10. lg, 56%) of the above structure.

MS [M + H] ⁺ = 547

Dissolve Compound I (20.00 g. 33.δ0ιιιιηο1) and Bromobenzene (5.26 g, 33.5 レ₀ 1) in 300 ml of tetrahydrofuran in a 500 ml equipotential bottom flask under nitrogen atmosphere, then add 2M aqueous potassium carbonate solution (150 ml). Tetrakis- (triphenylphosphine) palladium (1.16 g, 1.00 μl) was added thereto, followed by heating and stirring for 3 hours. Lower the temperature to room temperature (23 ± 5 ^° C) and remove the water layer. After drying over anhydrous magnesium sulfate and concentrated under reduced pressure ᅳ recrystallized with 180ml ethyl acetate to give a compound 22 (11.5g, 60%) of the above structure.

MS [M + H] ⁺ = 572

Compound J (20.00 g, 33.50 mmol) in a 500 ml equipotential bottom flask in a nitrogen atmosphere. After completely dissolving bromo benzene (5.26 g, 33.50 μl) in 300 ml of tetrahydrofuran, 2 M aqueous potassium carbonate solution (150 nil) was added, followed by tetrakis- (Triphenylphosphine) palladium (1.16 g. 1.00 x iol) was added thereto, followed by heating and stirring for 3 hours. Lower the temperature to room temperature (23 ± 5 ^° C) and remove the water worms. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure and recrystallized with 180 ml of ethyl acetate to obtain Compound 23 (11.5 g, 60%) having the above structure.

MS [M + H] ⁺ = 572

A glass substrate coated with a thin film having an indium tin oxide (IT0) of 1.000 A was placed in distilled water in which a detergent was dissolved, and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Mi 11 ipore Co. was used as distilled water. After ΙΤ0 was washed for 30 minutes, ultrasonic washing was performed twice with distillation and water for 10 minutes. After the distilled water was washed, isopropyl alcohol was ultrasonically washed with acetone and methane with a solvent, dried and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The following compound [HI ᅳ A] was thermally vacuum deposited to a thickness of 600 A on the prepared IT0 transparent electrode to form a hole injection layer. 50 A and the following compound, [HT-A] (600 A), were sequentially vacuum deposited on the hole injection layer to form nuclei nitrile nucleated azatriphenylene (HAT), thereby forming a hole transport layer.

Subsequently, the following compounds [BH] and [BD] were vacuum-deposited at a weight ratio of 25: 1 on the hole transport layer to have a film thickness of 200 A to form a light emitting layer.

Compound 1 prepared in Preparation Example 1 and the following compound [LiQKLithiumquinolate) were vacuum-deposited at a weight ratio of 1: 1 on the emission layer to form an electron injection and transport layer at a thickness of 350A. Lithium fluoride (LiF) and 1.000 A thick aluminum were sequentially deposited on the electron injection and transport layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.9 A / sec, and the lithium fluoride at the cathode was 0.3 A / sec _. Aluminum maintained a deposition rate of .2 A / sec, and the vacuum degree during deposition was 1 X 10-7 to 5 10-8 torr.

 <Examples 1-2 to 1-23>

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except for using the compound shown in Table 1 below instead of compound 1 in Example 1-1.

Example 1-1 device was manufactured except that Compound (I) having the following structure was used instead of Compound 1 in Example 1-1.

Example 1-1 device was fabricated except that compound (II) having the following structure was used instead of compound 1 in Example 1-1.

In Example ^1-1, the organic light emitting device was manufactured in the same manner as in Example 1-1 except that instead of compound 1 to use the compound (III) in the structure. ^{^{zn (960Ό 'z' o)}} SS '9 Z' Zl Ζΐ-ΐ [btv ^

OST (660Ό ^' zn ^' O) TC ^' TI Π-ΐ [blv ^ τζτ (960

O ^' ζ ^' θ) 0T Οΐ-Τ [lv ^ oss 6 6-T [[v ^

Z9l (960Ό K ^t 0) 8 8 I

^{^{I9T (960Ό 'ΖΠ' Ο)}} L ZT

69T (6600 ^' ΖΠΌ) 9 9-TH ^

6 (960Ό ᅳ ^' o) 0S ^' 9 SS

102 (Ζ60Ό Ί0) ZT ^' 9 SS ^

I9T (660 Ό 'm ^' 0) TS ^' 9 £ ε-τ [bk ^ o (9600 Ί 0) ½r

09T (960Ό '0) _^ ζε s LZ ^' V ΐ τ-τ W ^

(IO

IB ⁰⁶工 / Vi «0T @ V / P3)

k--ii ^ l ^ k [bS-T [ ¹ IT [Hifl ^ 'CS-T th TI [\ P [Y ^ -t ° _Y

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Comparative Example 1-1 I 4.67 3.94 o o o o o o 97

寸

Comparative Example 1-2 II 4.56 4.11 (0.15 ^I X ⁾ 1, 0.110) 110 o O

o ο ο

o o o o o

Comparative Example 1-3 III 4.57 4.15 O ο ο

o 105 1O ^ι-

!,,, ^'- ^ «it can be seen that from the results of Table 1, by interrogating ring compound represented by the formula (1) can be used for the organic layer to the electron injection and electron transport of the organic light-emitting device at the same time.

When Examples VII to 23 and Comparative Example 1-1 are compared, the compound substituted with only one side of the fluorene skeleton as shown in the general formula (1). The driving voltage in the organic light emitting device as compared to the compound having a substituent symmetrically on both sides of the fluorene skeleton. It can be seen that it shows better characteristics in terms of efficiency and lifespan. These results indicate that the heterocyclic compound represented by Formula 1 has excellent thermal stability, 6.0. Deep H0M0 level above eV. This is because it has high triplet energy (ET) and hole stability.

When Examples 1 to 5 to 1-8 and Comparative Examples 1 to 2 and 1 to 3 were compared, when the fluorene skeleton had an anthracene-based substituent as in the compound (II) or (III) As a result, the color purity is significantly reduced. This is because the anthracene-based luminescence properties also affect the fluorene skeleton. In particular, Example 1-1. 1-8, 1-9, 1-10, 1-12. In the case of the hetero compounds included in 1-13 and 1-19, the HOMO energy was deeper than 6.1 eV, and thus the electron mobility was high. Therefore, the hetero compounds contained in 1-13 and 1-19 exhibited superior characteristics in terms of driving voltage, efficiency, and lifetime.

In addition, when the heterocyclic compound represented by Chemical Formula 1 is used in an organic material layer capable of simultaneously injecting electrons and transporting electrons, it is possible to mix and use n-type dopants used in the art. Accordingly, the heterocyclic compound represented by Formula 1 has a low driving voltage and high efficiency, and may improve stability of the device by hole stability of the compound.

Example 2

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1.000A was placed in distilled water in which a detergent was dissolved and ultrasonically washed. At this time, Fischer Co. was used as a detergent. As distilled water, distilled water filtered secondly was used as a filter manufactured by Miller 11 (Mi 11 ipore Co.). After washing IT0 for 30 minutes, the ultrasonic washing was performed for 10 minutes by repeating the two distilled water. After the distilled water was washed, isopropyl alcohol was ultrasonically washed with a solvent of acetone and methanol, dried, and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

Compound [HI-A] was vacuum-deposited to a thickness of 600 A on the πΌ transparent electrode thus prepared to form a hole injection layer. Nuclear nitrile nucleoaza E riphenylene (HAT) 50 A and compound [HT-A] (600A) were sequentially vacuum deposited on the hole injection layer to form a hole transport layer.

Subsequently, compounds [BH] and [BD] were deposited on the hole transport layer at a thickness of 200 A.

The light emitting layer was formed by vacuum deposition at a weight ratio of 25: 1.

Compound 1 prepared in Preparation Example 1 was vacuum-deposited on the emission layer to form an electron control layer with a thickness of 200 A. The following compound [ET-1-J] and the compound [LiQKLithiimiquinolate) were vacuum-deposited in a 1: 1 increase ratio on the electron control layer to form an electron injection and transport layer at a thickness of 150A. The electron injection and transport layer Lithium fluoride (Li F) and Ι, ΟΟΟΑ thickness of 10A thickness were sequentially deposited on the cathode to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.9 A / sec. The lithium fluoride of the negative electrode was 0.3 A / sec. Aluminum maintained a deposition rate of 2 A / sec, and the vacuum degree during deposition was maintained at 1 X ΚΓ ⁷ to 5 X 10 ^s torr. abandonment

Compound 2 shown in Table 2 instead of Compound 1 in Example 2-1 Except to use. An organic light emitting device was manufactured in the same manner as in Example 2-1.

Example 2-1 device was fabricated except that compound (I) having the above structure was used instead of compound 1 in Example 2-1.

Example 2-1 device was manufactured except that Compound (II) having the structure shown below was used instead of Compound 1 in Example 2-1.

Comparative Example 2-3

An organic light emitting diode was manufactured according to the same method as Example 2-1 except for using Compound (III) having the following structure instead of Compound 1 in Example 2-1.

[Z Έ] OS 玉^' a ^^

1 tt

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From the results of Table 2, it can be seen that the heterocyclic compound represented by the formula (1) can be used in the electronic control insect of the organic light emitting device. Moreover, when Example 2—1 to 2-23 is compared with Comparative Example 2-1. Compounds substituted with only one side in the fluorene skeleton as in Chemical Formula 1 are excellent in thermal stability, and have a deep H0M0 level of 6. 0 eV or more. Driving voltage in an organic light emitting device as compared to a compound having a high triplet energy (ET), and hole stability, symmetrically substituted on both sides in the fluorene skeleton. It can be seen that it shows excellent characteristics in terms of efficiency and lifespan.

In addition. When Example 2—1 to 2-23 and Comparative Examples 2-2 and 2—3 are compared, Unlike compound (II) or (III) having anthracene as a substituent, compounds 1 to 23 in Examples 2-1 to 2-23 can be confirmed to have high color purity.

[Explanation of code]

1 ： Substrate 2 ： Anode

3: light emitting layer 4: cathode

5: Hole injection layer 6: Hole transport layer

7: emitting layer 8: electron transport layer

Claims

[Claim]

[Claim 11

A compound of formula

'

In Chemical Formula 1,

A is C6-C20 aryl unsubstituted or substituted with a cyano group or a diphenylphosphine oxide group; Fluorenyl unsubstituted or substituted with a cyano group; And it is selected from the group consisting of heteroaryl containing 2 to 9 carbon atoms containing at least one N,

Ar ₂ is selected from the group consisting of functional groups of Formulas 2a to 2e,

[Formula 2c]

In Chemical Formulas 2a to 2e,

Ar ₃ to Ar ₅ are each independently hydrogen; Distillate; Alkyl having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Or 0. Heteroaryl having 2 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, Si and S.

And L ₂ are each independently bonded; Or substituted or unsubstituted phenylene

Rt and ¾ are each independently. Hydrogen; heavy hydrogen; halogen; Saano; Nitro; Amino; Substituted or unsubstituted alkyl having 1 to 60 carbon atoms; Substituted or unsubstituted haloalkyl having 1 to 60 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 60 carbon atoms; Substituted or unsubstituted haloalkoxy having 1 to 60 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 60 carbon atoms; Substituted or unsubstituted alkenyl having 2 to 60 carbon atoms; Substituted or unsubstituted aryl having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 60 carbon atoms; Or substituted or unsubstituted, heteroaryl having 2 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of 0, N, Si and S,

a and b are each independently an integer of 0 to 3, and c is an integer of 0 or 1. [Claim 2]

The method of claim 1.

The compound of Formula 1 is represented by the following formula

Compounds having the structure:

In the above formula la to lc,

Xi and ¾ are either — and —L ₂ — Ar ₂ , but not identical to each other, and ^■

Ri; R ₂ , Li, L ₂ . An. Ar ₂ , a and b are as defined in claim 1.

[Claim 3]

The method of claim 1. .

A is substituted with a cyano group or a diphenylphosphine oxide group or Unsubstituted, phenyl, naphthalenyl. Anthracenyl. Phenanthrenyl, fluorenyl, pyridinyl ᅳ pyridazinyl, pyrimidinyl, triazinyl. Benzopyridinyl, benzopyridazinyl, ^' benzopyrimidinyl and benzopyridinyl ^' . compound.

[Claim 4]

The method of claim 1.

An is any one selected from the group consisting of

In the structural formulas. m and n are each independently Is an integer.

[Claim 5]

The method of claim 1.

L ′ and —L ₂ —Ar ₂ have a different structure from each other.

[Claim 6]

The method of claim 1.

Ar ₃ to Ar ₅ are each independently hydrogen, methyl or phenyl.

[Claim 7]

The method of claim 1,

Any one selected from the group consisting of the following compounds: compound.

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IIS06T / 8101 ΟΛ oz

Ϊ176Ζ00 / 8Ϊ0ΖΗΜ / Χ3 <Ι ZZS06l / 8T0Z OAV

Ϊ176Ζ00 / 8Ϊ0ΖΗΜΧ3 <Ι ZL

Ϊ176Ζ00 / 8Ϊ0ΖΗΜ / Χ3 <Ι ZZS06l / 8T0Z OAV

Ϊ176Ζ00 / 8Ϊ0ΖΗΜ / Χ3 <Ι ZZS06l / 8T0Z OAV VL

Ϊ176Ζ00 / 8Ϊ0ΖΗΜ / Χ3 <Ι ZZS06l / 8T0Z OAV

Ϊ176Ζ00 / 8Ϊ0ΖΗΜ / Χ3 <Ι ZZS06l / 8T0Z OAV

[Claim 8]

A first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the low U electrode and the second electrode.

At least one layer of the organic insects containing the compound according to any one of claims 1 to 7. Organic light emitting device.