KR101627743B1 - Compound, light emitting diode, organic optoelectric device, and display device - Google Patents

Abstract

(상기 화학식 Ⅰ에서, R¹ 내지 R⁵, X¹, 및 X²의 정의는 명세서에 정의된 바와 같다.)And a display device including the organic optoelectronic device. The present invention provides a compound represented by the following formula (I).
(I)

(In the above formula (I), the definitions of R ¹ to R ⁵ , X ¹ , and X ² are as defined in the specification.)

Description

TECHNICAL FIELD The present invention relates to a compound, a light emitting material containing the same, an organic optoelectronic device, and a display device including the organic optoelectronic device. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

Compound, a light emitting material containing the same, an organic optoelectronic device, and a display device including the organic optoelectronic device.

Organic optoelectronic devices are devices that can switch between electrical and optical energy.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle. One is an optoelectronic device in which an exciton formed by light energy is separated into an electron and a hole, the electron and hole are transferred to different electrodes to generate electric energy, and the other is a voltage / Emitting device that generates light energy from energy.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, and organic photo conductor drums.

In recent years, organic light emitting diodes (OLEDs) have attracted considerable attention due to the demand for flat panel display devices. The organic light emitting diode is a device for converting electrical energy into light by applying an electric current to the organic light emitting material, and usually has an organic layer inserted between an anode and a cathode. The organic layer may include a light emitting layer and an optional auxiliary layer. The auxiliary layer may include, for example, a hole injecting layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, And a hole blocking layer.

The performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and the organic layer is highly affected by the organic material contained in the organic layer.

In particular, in order for the organic light emitting device to be applied to a large-sized flat panel display device, it is necessary to develop an organic material capable of increasing the mobility of holes and electrons and increasing the electrochemical stability.

High efficiency, long life, and the like.

A light emitting material containing the compound, an organic optoelectronic device, and a display device including the organic optoelectronic device.

In one embodiment of the present invention, there is provided a compound represented by the following general formula (I).

(I)

In the above formula (I)

R ¹ and R ² are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, R ¹ and R ² Is a substituted or unsubstituted C1 to C10 alkyl group,

R ³ to R ⁵ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, A substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof, wherein the substituent is a C1 to C10 alkyl group, a silyl group, a halogen group, a cyano group, a hydroxy group, a nitro group, a carboxyl group ,

X ¹ and X ² are each independently a single bond or NLT, and X ¹ And X < ² > is NLT,

L is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C3 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C3 to C30 heteroarylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group,

T represents hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C3 to C30 heteroaryl group.

In another embodiment of the present invention, the anode, cathode and

And at least one organic layer positioned between the anode and the cathode,

The organic layer provides an organic optoelectronic device including the above-described compound.

In another embodiment of the present invention, there is provided a luminescent material comprising the above compound.

In another embodiment of the present invention, there is provided a display device including the above-described organic optoelectronic device.

A high-efficiency, long-life organic optoelectronic device can be realized.

1 and 2 are sectional views showing an organic light emitting device according to an embodiment, respectively.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, at least one of the substituents or at least one hydrogen in the compound is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, C1 to C10 alkyl groups such as a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, A trifluoroalkyl group or a cyano group.

A substituted or unsubstituted C1 to C20 amine group, a nitro group, a substituted or unsubstituted C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C10 alkylsulfinyl group, A C1 to C10 trifluoroalkyl group such as a C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group or a trifluoromethyl group, or a cyano group may be fused together to form a ring . Specifically, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

Means one to three heteroatoms selected from the group consisting of N, O, S and P in one functional group, and the remainder is carbon, unless otherwise defined.

In the present specification, the term "combination thereof" means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.

As used herein, the term "alkyl group" means an aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an alkyl group having from 1 to 20 carbon atoms. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are included in the alkyl chain and include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec- Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And the like.

The term "aryl group" used herein means a substituent in which all the elements of the cyclic substituent have p-orbital and the p-orbital forms a conjugation, and the monocyclic or fused-ring polycyclic (I. E., A ring that divides adjacent pairs of carbon atoms) functional groups.

As used herein, the term " heteroaryl group "means that the aryl group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heteroaryl group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthra A substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, A substituted or unsubstituted aryl group, a substituted m-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group , A substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted pyrazolyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, Substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted thiazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzimidazolyl, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinazolinyl group, Substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted benzoxazinyl groups, substituted or unsubstituted benzothiazyl groups, substituted or unsubstituted acridinyl groups, Substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted carbazolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted pyrazolyl groups, Diary, or a combination thereof.

In the present specification, the hole property refers to a property of forming holes by donating electrons when an electric field is applied, and has a conduction property along the HOMO level so that the injection of holes formed in the anode into the light emitting layer, Quot; refers to the property of facilitating the movement of the hole formed in the light emitting layer to the anode and the movement of the hole in the light emitting layer.

In addition, the electron characteristic refers to a characteristic that electrons can be received when an electric field is applied. The electron characteristic has a conduction characteristic along the LUMO level so that electrons formed in the cathode are injected into the light emitting layer, electrons formed in the light emitting layer migrate to the cathode, It is a characteristic that facilitates movement.

The organic compounds according to one embodiment will be described below.

In one embodiment of the present invention, a compound represented by the following formula (I) may be provided.

(I)

In the above formula (I)

R ¹ and R ² are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, R ¹ and R ² Is a substituted or unsubstituted C1 to C10 alkyl group,

R ³ to R ⁵ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, A substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof, wherein the substituent is a C1 to C10 alkyl group, a silyl group, a halogen group, a cyano group, a hydroxy group, a nitro group, a carboxyl group ,

X ¹ and X ² are each independently a single bond or NLT, and X ¹ And X < ² > is NLT,

L is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C3 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C3 to C30 heteroarylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group,

T represents hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C3 to C30 heteroaryl group.

The compound according to one embodiment of the present invention has a structure that interferes with the electron flow of a conjugated system, thereby providing a high triplet level suitable for light emission and minimizing the occurrence of a structural isomer during synthesis Thereby increasing the purity.

In addition, by introducing an alkyl substituent in at least one of R ¹ and R ^2, R ^1, and R and ² can both be improved in stability as compared with the case substituted by hydrogen, R ¹ and R ² are both substituted with an aromatic substituent It is possible to deposit at a relatively low temperature by reducing the molecular weight, thereby reducing the thermal stress to which the compound is subjected during the process, thereby improving the device reliability.

The above formula (I) may be represented by the following formula (II) or (III)

[Formula II] [Formula (III)

In the above formulas (II) and (III)

R ¹ to R ⁵ , L and T are the same as defined in claim 1.

R ¹ and R ² may be a substituted or unsubstituted C1 to C10 alkyl group.

The T may be a compound listed in Group I below.

[Group I]

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In said group I,

R, R 'and R ¹⁰¹ to R ¹⁰⁵ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 silyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a combination thereof,

* Is a connecting point and may be located in any of the elements forming the functional group.

Specifically, T may be one listed in Group II below.

[Group II]

In the group II,

Z is each independently N or CR ^a , at least one of Z is N,

W is independently N, O, S, SO, SO ₂ , CR ^b , CR ^c R ^d , SiR ^e or SiR ^f R ^g ,

Wherein R ^a and R ^b to R ^g are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C3 to C30 heterocycloalkyl groups , A substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C3 to C30 heteroaryl group,

* Is a connecting point and may be located in any of the elements forming the functional group.

For example, the T may be as listed in Group II-1 below:

[Group II-1]

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In the group II-1,

R or R 'is hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group,

* Is a connecting point and may be located in any of the elements forming the functional group.

Such compounds may be, but are not limited to, those listed in Group III below:

[Group III]

According to another embodiment of the present invention, there can be provided a light emitting material comprising a first compound, wherein T is a functional group having a hole property, and a second compound having an electron characteristic, in the formula (1). More specifically, the first compound is any one of those listed in Group I in Formula 1 and the second compound is any one of those listed in Group II, specifically Group II-1, in Formula 1 have.

The first compound and the second compound may be contained in a molar ratio of 9: 1 to 1: 9.

The first compound and the second compound are used as a first host compound and a second host compound, respectively, and may further include a dopant.

Hereinafter, the organic optoelectronic device to which the compound or the light emitting material described above is applied will be described.

The organic optoelectronic device is not particularly limited as long as it is an element capable of converting electric energy and optical energy. Examples of the organic optoelectronic device include organic light emitting devices, organic solar cells, and organic photoconductor drums.

Here, an organic light emitting device, which is an example of an organic optoelectronic device, will be described with reference to the drawings.

1 and 2 are cross-sectional views illustrating an organic light emitting device according to an embodiment.

1, an organic optoelectronic device 100 according to an embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 located between the anode 120 and the cathode 110 .

The anode 120 may be made of a conductor having a high work function to facilitate, for example, hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 is made of a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of ZnO and Al or a metal and an oxide such as SnO ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene), polypyrrole and polyaniline, It is not.

The cathode 110 may be made of a conductor having a low work function, for example, to facilitate electron injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 is made of a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium or the like or an alloy thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al and BaF ₂ / Ca.

The organic layer 105 includes the light-emitting layer 130 including the above-described organic compound.

The light-emitting layer 130 may include, for example, the organic compound alone, or may be a mixture of at least two of the organic compounds described above, or may include a mixture of the above-described organic compound and another compound. When the above-mentioned organic compound is mixed with another compound, it may be contained in the form of, for example, a host and a dopant, and the above-mentioned organic compound may be included, for example, as a host. The host may be, for example, a phosphorescent host or a fluorescent host, for example, a phosphorescent host.

When the above-mentioned organic compound is included as a host, the dopant may be an inorganic, organic, or organic compound and may be selected from known dopants.

Referring to FIG. 2, the organic light emitting diode 200 further includes a hole assist layer 140 in addition to the light emitting layer 230. The hole assist layer 140 can further enhance the hole injection and / or hole mobility between the anode 120 and the light emitting layer 230 and block the electrons. The hole-assist layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer. The organic compound described above may be included in the light emitting layer 230 and / or the hole auxiliary layer 140.

1 or 2, the organic thin film layer 105 may further include an electron transport layer, an electron injection layer, a hole injection layer, and the like.

The organic light emitting devices 100 and 200 may be formed by forming an anode or a cathode on a substrate and then performing a dry deposition method such as evaporation, sputtering, plasma plating, and ion plating; Or a wet film formation method such as spin coating, slit coating, dipping, flow coating, and inkjet printing, or the like to form an organic layer thereon, A negative electrode or a positive electrode.

The organic light emitting device described above can be applied to an organic light emitting display.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

(Preparation of compound for organic optoelectronic device)

Example  1: Synthesis of compound 15

Step 1: Synthesis of intermediate 1-1

[Reaction Scheme 1]

4-bromo-9,9-dimethyl-fluorene 71.2g (260.64 mmol), aniline 30g (217.20 mmol) _{2-nitro, Pd 2 (dba 3) 5.97g} (6.52 mmol), a tree (t- butyl) 15.5 mL (32.58 mmol) of phosphine (50% in toluene), 31.3 g (325.80 mmol) of sodium (t-butoxide) and 200 mL of toluene were added and heated at 110 캜 for 12 hours under nitrogen gas and stirred. The reaction was terminated by TLC and then cooled at room temperature. After filtration, it was washed several times with distilled water and methanol. The resulting solid was dissolved in dichlorobenzene and recrystallized from methanol to obtain 49.5 g of Intermediate 1-1 (9,9-dimethyl-N- (2-nitrophenyl) -9H-fluoren- 68.98%).

Step 2: Synthesis of intermediate 1-2

[Reaction Scheme 2]

49.5 g (149.83 mmol) of Intermediate 1-1, 189.6 g (449.48 mmol) of tin chloride, and 1000 mL of ethanol were added, and the mixture was heated to 70 DEG C for 12 hours and stirred. The reaction was terminated by TLC and then cooled at room temperature. After separating the ethanol under reduced pressure, the solid was precipitated by neutralizing with 1N sodium hydroxide solution. The precipitated solid was filtered, dissolved in toluene, extracted and washed with distilled water. Residual water was removed with magnesium sulfate, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 32.41 g (yield: 72%) of Intermediate 1-2 in the solid state.

Step 3: Synthesis of intermediate 1-3

[Reaction Scheme 3]

32.4 g (107.86 mmol) of Intermediate 1-2, 30 mL of sulfuric acid and 300 mL of acetic acid were added, and the mixture was stirred at 10 ° C for 10 minutes. Then, 7.6 g (110.01 mmol) of sodium nitrate was dissolved in 162 mL of distilled water to make an aqueous solution, and the solution was gradually added dropwise to the flask containing the reaction product for 15 minutes. After further stirring for 10 minutes, the mixture was stirred at 130 DEG C for 20 minutes. After completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature and 250 mL of distilled water was added. The precipitated solid was filtered, rinsed with methanol, and purified with a column packed with silica gel. (Mobile phase: dimethyl chloride) was distilled off under reduced pressure using a rotary evaporator, then dissolved again in dimethyl chloride, and recrystallized from ethanol. After filtration and drying, 19.87 g (yield: 65%) of Intermediate 1-3 was obtained.

Step 4: Synthesis of final compound (Compound 15)

[Reaction Scheme 4]

19.87 g (70.12 mmol) of Intermediate 1-3 synthesized according to Step 3, 13.21 g (84.14 mmol) of bromobenzene, 1.93 g (2.10 mmol) of Pd ₂ (dba) ₃ , (10.52 mmol), sodium (t-butoxide) 10.11 g (105.18 mmol) and para-xylene (200 mL) were added and heated at 110 캜 for 12 hours under nitrogen gas and stirred. The reaction was terminated by TLC and then cooled at room temperature. After filtration, it was washed several times with distilled water and methanol. The resulting solid was dissolved in dichlorobenzene and recrystallized from methanol to obtain 17.64 g (yield: 70%) of compound 15 as a final compound.

The compound 15 was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 359.46, Found: 360.17

Example  2: Synthesis of compound 1

Step 5: Synthesis of intermediate 2-1

[Reaction Scheme 5]

9,9-dimethyl-fluoren-4-yl Boro Nick acid 55g (231.01 mmol), 1- bromo-2-nitro benzene 56g (277.21 mmol), Pd ( pph 3) 4 5.34g (4.62 mmol), potassium (462.01 mmol), tetrahydrofuran (770 mL) and distilled water (385 mL) were added. The mixture was heated at 100 占 폚 under a stream of nitrogen for 16 hours and stirred. After completion of the reaction is confirmed by TLC, the organic layer and the distilled water layer are separated using an extraction funnel. The solvent of the organic layer was removed by vacuum distillation using a rotary evaporator, dissolved in 300 mL of dimethyl chloride, and added dropwise to 1000 mL of n-hexane to obtain a solid. After filtration and drying, 43.71 g (yield: 60%) of Intermediate 2-1 was obtained.

Step 6: Synthesis of intermediate 2-2

[Reaction Scheme 6]

43.71 g (138.6 mmol) of Intermediate 2-1 obtained in Step 5, and 115.15 g (693 mmol) of triethylphosphite were placed, and the mixture was heated and stirred at 120 DEG C for 12 hours. After completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature, stirred, and added dropwise to distilled water. Ethyl acetate was added and dissolved in the mixture. The distilled water layer and the organic layer were separated using a separating funnel. The separated organic layer was concentrated using a rotary evaporator to separate the silica gel column. (Mobile phase: ethyl acetate: hexane = 1: 1) to obtain 23.56 g (yield: 60%) of intermediate 2-2 after removal of the solvent.

Step 7: Synthesis of final compound (Compound 1)

[Reaction Scheme 7]

The procedure of Step 4 was repeated except that Intermediate 2-2 obtained in Scheme 6 was used instead of Intermediate 1 obtained in Scheme 3 to obtain 20.92 g (Yield: 70%) of Compound 1.

The synthesized compound was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 359.46, measured: 360.15

Example  3: Synthesis of Compound 79

[Reaction Scheme 8]

The compound 79 was synthesized by the same procedure as in the step 4, except that bromo-4,6-diphenyl-1,3,5-triazine (26.27 g) was used instead of the bromobenzene of the reaction scheme 4 to obtain 25.26 g (Yield: 70%).

The synthesized compound was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 514.62, Found: 515.22

Example  4: Synthesis of Compound 61

[Reaction Scheme 9]

The compound 61 was synthesized by the same procedure as in the step 7, except that bromo-4,6-diphenyl-1,3,5-triazine (26.27 g) was used instead of the bromobenzene of the formula 7 to obtain 25.98 g Yield: 72%).

The synthesized compound was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 514.62, Found: 515.23

Comparative Example  1: Synthesis of Comparative Compound 1

Step 1: Synthesis of Comparative Intermediate 1-1

[Reaction Scheme 10]

Except that 4-bromo-9,9-diphenylfluorene (69.03 g) was used instead of 4-bromo-9,9-dimethylfluorene in Scheme 1, Comparative Intermediate 1-1 was synthesized to obtain 49.36 g (yield: 75%) of Comparative Intermediate 1-1.

Step 2: Synthesis of Comparative Intermediate 1-2

[Reaction Scheme 11]

Comparative Intermediate 1-2 was synthesized in the same manner as in Step 2 except that Intermediate 1-1 (49.36 g) was used instead of Intermediate 1-1 in Reaction Scheme 2 to obtain 31.81 g of Comparative Intermediate 1-2 (Yield: 69%).

Step 3: Synthesis of Comparative Intermediate 1-3

[Reaction Scheme 12]

Comparative Intermediate 1-3 was synthesized by the same procedure as in Step 3 except that Comparative Intermediate 1-2 (31.81 g) was used instead of Intermediate 1-2 in Scheme 3 to obtain 21.38 g of Comparative Intermediate 1-3 Yield: 70%).

Step 4: Synthesis of Comparative Compound 1

[Reaction Scheme 13]

17.25 g (Yield: 68%) of Comparative Compound 1 was obtained by the same procedure as in Step 4, except that Comparative Intermediate 1 -3 (21.38 g) was used instead of Intermediate 1 -3 in Scheme 4.

The synthesized compound was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 483.60, Found: 484.20

Comparative Example  2: Synthesis of Comparative Compound 2

Step 5: Synthesis of Comparative Intermediate 2-1

[Reaction Scheme 14]

Except that 9,9-diphenylfluorene-4-ylboronic acid (60.00 g) was used instead of 9,9-dimethylfluoren-4-ylboronic acid in Scheme 5, By the same procedure, 45.86 g (yield: 63%) of Comparative Intermediate 2-1 was obtained.

Step 6: Synthesis of Comparative Intermediate 2-2

[Reaction Scheme 15]

25.52 g (yield: 60%) of Comparative Intermediate 2-2 was obtained by the same procedure as in Step 6 except that Intermediate 2-1 (45.86 g) was used instead of Intermediate 2-1 in Scheme 6 .

Step 7: Synthesis of Comparative Compound 2

[Reaction Scheme 16]

21.50 g (Yield: 71%) of Comparative Compound 2 was obtained by the same procedure as in Step 7, except that Comparative Intermediate 2-2 (25.52 g) was used instead of Intermediate 2-2 in Scheme 7.

The synthesized compound was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 483.60, Found: 484.17

Comparative Example  3: Synthesis of Comparative Compound 3

[Reaction Scheme 17]

Synthesis was conducted in the same manner as in Step 8 except that Intermediate Compound 1-3 (21.38 g) was used instead of Intermediate Compound 1-3 in Scheme 8 to obtain 22.45 g (Yield: 67%) of Comparative Compound 3.

The synthesized compound was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 638.76, Found: 639.25

Comparative Example  4: Synthesis of Comparative Compound 4

[Reaction Scheme 18]

By the same procedure as in Step 9, 27.60 g (Yield: 69%) of Comparative Compound 4 was obtained, except that Comparative Intermediate 2-2 (25.52 g) was used instead of Intermediate 2-2 in Scheme 9.

The synthesized compound was analyzed by a mass spectrometer (LC Mass Spectroscopy), and the results were as follows.

Calculated value  : 638.76, Found: 639.25

(Fabrication of organic light emitting device)

Example  5

Compound 15 obtained in Example 1 was used as a host and Ir (PPy) ₃ was used as a dopant to prepare an organic light emitting device.

As the anode, ITO was used in a thickness of 1000 Å, and as a cathode, aluminum (Al) was used in a thickness of 1000 Å. Specifically, an explanation will be given of a method of manufacturing an organic light emitting device. An ITO glass substrate having a sheet resistance of 15 Ω / cm ² is cut into a size of 50 mm × 50 mm × 0.7 mm, and is cut in acetone, isopropyl alcohol and pure water After ultrasonic cleaning for 15 minutes each, UV ozone cleaning was performed for 30 minutes.

N4, N4'-di (naphthalen-1-yl) -N4, N4'-diphenylbiphenyl-4,4'-diamine ( NPB) (80 nm) was deposited thereon to form a hole transporting layer of 800 ANGSTROM. Subsequently, using the compound 1 obtained in Example 1 under the same vacuum deposition condition, a light emitting layer with a thickness of 300 angstroms was formed, and Ir (PPy) ₃ , which is a phosphorescent dopant, was simultaneously deposited thereon. At this time, the deposition rate of the phosphorescent dopant was adjusted so that the phosphorescent dopant content was 7% by weight when the total amount of the light emitting layer was 100% by weight.

Bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum (BAlq) was deposited on the light emitting layer using the same vacuum deposition conditions to form a hole blocking layer having a thickness of 50 Å. Subsequently, Alq3 was deposited under the same vacuum deposition conditions to form an electron transport layer having a film thickness of 200 ANGSTROM. LiF and Al were sequentially deposited on the electron transport layer as cathodes to fabricate an organic photoelectric device.

The structure of the organic photoelectric device was ITO / NPB (80 nm) / EML (Compound 15 (93 wt%) + Ir (PPy) ₃ (7 wt%), 30 nm) / Balq (5 nm) / Alq3 ) / LiF (1 nm) / Al (100 nm).

Example  6

An organic luminescent device was prepared in the same manner as in Example 5 except that the compound 1 of Example 2 was used instead of the compound 15 of Example 1.

Example  7

An organic luminescent device was prepared in the same manner as in Example 5 except that the compound 79 of Example 3 was used instead of the compound 15 of Example 6.

Example  8

An organic luminescent device was prepared in the same manner as in Example 5 except that the compound 61 of Example 4 was used instead of the compound 1 of Example 1.

Example  9

An organic light emitting device was prepared in the same manner as in Example 5 except that the compound 15 of Example 1 and the compound 79 of Example 3 were evaporated at the same rate and in a ratio of 1:

Example  10

An organic luminescent device was prepared in the same manner as in Example 9, except that the compound 1 of Example 2 and the compound 61 of Example 4 were used instead of the compound 15 of Example 1 and the compound 79 of Example 3, respectively.

Comparative Example  5

An organic luminescent device was prepared in the same manner as in Example 5, except that Comparative Compound 1 of Comparative Example 1 was used instead of Compound 15 of Example 1.

Comparative Example  6

An organic light emitting device was prepared in the same manner as in Example 5, except that the compound 15 of Comparative Example 2 was used instead of the compound 15 of Example 1.

Comparative Example  7

An organic luminescent device was prepared in the same manner as in Example 5, except that the compound 15 of Comparative Example 3 was used instead of the compound 15 of Example 1.

Comparative Example  8

An organic luminescent device was prepared in the same manner as in Example 5, except that Comparative Compound 4 of Comparative Example 4 was used instead of Compound 15 of Example 1.

Comparative Example  9

An organic luminescent device was prepared in the same manner as in Example 9, except that the compound 15 of Comparative Example 1 and the comparative compound 3 of Comparative Example 3 were used instead of the compound 15 of Example 1 and the compound 79 of Example 3.

Comparative Example  10

An organic light emitting device was fabricated in the same manner as in Example 9 except that the compound 15 of Example 1 and the compound 4 of Comparative Example 2 were used instead of the compound 79 of Example 3.

(Performance Evaluation of Organic Light Emitting Device)

The current density change, the luminance change, and the light emitting efficiency of the organic light emitting device according to Examples 5 to 10 and Comparative Examples 5 to 10 were measured according to the voltage.

The specific measurement method is as follows, and the results are shown in Table 1.

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm ² ) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

No. compound The driving voltage (V) Color (EL color) Efficiency (cd / A) Example 5 Compound 15 5.7 Green 24.8 Example 6 Compound 1 5.7 Green 25.2 Example 7 Compound 79 4.8 Green 30.3 Example 8 Compound 61 4.7 Green 31.8 Example 9 Compound 15 + Compound 79 4.2 Green 51.2 Example 10 Compound 1 + Compound 61 3.9 Green 53.7 Comparative Example 5 Comparative compound 1 8.3 Green 1.7 Comparative Example 6 Comparative compound 2 7.9 Green 5.6 Comparative Example 7 Comparative compound 3 7.7 Green 13.3 Comparative Example 8 Comparative compound 4 7.7 Green 15.9 Comparative Example 9 Comparative Compound 1 + Comparative Compound 3
(1: 1) 6.5 Green 36.8 Comparative Example 10 Comparative Compound 2 + Comparative Compound 4
(1: 1) 6.9 Green 35.9

According to Table 1, the organic light emitting devices according to Examples 5 to 10 have significantly improved luminous efficiency and lifetime as compared with the organic light emitting devices according to Comparative Examples 5 to 10. [

Specifically, the compounds used in the organic light emitting devices according to Examples 5 to 10 were different from the compounds used in the organic light emitting devices according to Comparative Examples 5 to 10, and included bimethyl instead of biphenyl to make it easier to transport electrons Structure. Accordingly, it can be confirmed that the driving voltage of the organic light emitting device according to Examples 5 to 10 is lower than that of the organic light emitting device according to Comparative Examples 5 to 10.

In addition, the compounds used in the organic light emitting devices according to Examples 9 and 10 have a bipolar characteristic by appropriately mixing a compound having a hole transporting property and a compound having an electron transporting property, so that the flow of holes and electrons can be appropriately balanced . Thus, it can be seen that the efficiency of the OLED according to the ninth embodiment and the OLED according to the ninth embodiment is significantly improved as compared with the OLED according to the ninth embodiment and the fifth embodiment.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100, 200: organic light emitting device 110: cathode
120: anode 105: organic thin film layer
130, 230: light emitting layer 140: hole assist layer

Claims (15)

A compound represented by the formula (I)
(I)

In the above formula (I)
R ¹ and R ² are substituted or unsubstituted C 1 to C 10 alkyl groups,
R ³ to R ⁵ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, wherein the substituent is a C1 to C10 alkyl group, a silyl group, a halogen group , A cyano group, a hydroxy group, a nitro group, a carboxyl group,
X ¹ and X ² are each independently a single bond or NLT, at least one of X ¹ and X ² is NLT,
L is a single bond or an unsubstituted C6 to C30 arylene group,
T is a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, or a substituted or unsubstituted triazinyl group. The method according to claim 1,
(I) is a compound represented by the following formula (II) or (III): < EMI ID =
[Formula II] [Formula (III)

,

In the above formulas (II) and (III)
R ¹ to R ⁵ , L and T are the same as defined in claim 1. delete delete The method according to claim 1,
Wherein T is one selected from the groups listed in the following Group II:
[Group II]

In the group II,
Z is each independently N or CR ^a , at least one of Z is N,
Wherein R ^a is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl Or a substituted or unsubstituted C3 to C30 heteroaryl group,
* Is a connecting point and may be located in any of the elements forming the functional group. The method according to claim 1,
Wherein T is one selected from the groups listed in Group II-1 below:
[Group II-1]

In the group II-1,
* Is a connecting point and may be located in any of the elements forming the functional group. The method according to claim 1,
A compound represented by one of the compounds listed below.
[Compound 61] [Compound 79]

,

The anode, cathode, and
And at least one organic layer positioned between the anode and the cathode,
Wherein the organic layer comprises the compound according to any one of claims 1, 2, and 5 to 7. 9. The method of claim 8,
Wherein the organic layer includes a light emitting layer,
Wherein the light emitting layer comprises the compound for an organic photoelectric device. 9. The method of claim 8,
Wherein the organic layer includes at least one auxiliary layer selected from a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer and a hole blocking layer,
Wherein the auxiliary layer comprises the compound. A light-emitting material comprising a first compound represented by the following formula (I) and a second compound according to the sixth aspect:
(I)

In the above formula (I)
R ¹ and R ² are substituted or unsubstituted C 1 to C 10 alkyl groups,
R ³ to R ⁵ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, wherein the substituent is a C1 to C10 alkyl group, a silyl group, a halogen group , A cyano group, a hydroxy group, a nitro group, a carboxyl group,
X ¹ and X ² are each independently a single bond or NLT, at least one of X ¹ and X ² is NLT,
L is a single bond or an unsubstituted C6 to C30 arylene group,
T is selected from the groups listed in Group I below,
[Group I]

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

In the group I,
R, R 'and R ¹⁰¹ to R ¹⁰⁵ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 silyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a combination thereof,
* Is a connecting point and may be located in any of the elements forming the functional group. 12. The method of claim 11,
Wherein the first compound and the second compound are contained in a molar ratio of 1: 9 to 9: 1. 12. The method of claim 11,
Wherein the first compound and the second compound are used as a first host compound and a second host compound, respectively,
A light emitting material further comprising a dopant. The anode, cathode, and
And a light emitting layer disposed between the anode and the cathode and comprising a light emitting material according to claim 11. A display device comprising the organic opto-electronic device according to claim 14.

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