KR102034192B1 - Phenanthroline-triazine compound and organic light emitting diode comprising the same - Google Patents

Abstract

The present invention relates to an phenanthroline-triazine compound and an organic electroluminescent device exhibiting excellent efficiency characteristics by including it in at least one organic layer.

Description

PHENANTHROLINE-TRIAZINE COMPOUND AND ORGANIC LIGHT EMITTING DIODE COMPRISING THE SAME}

This application has been filed with some application fees through the 2017 Global Hidden Champions Autonomous Program hosted by the Gyeonggi-do Economic Research Institute.
The present invention relates to a phenanthroline-triazine compound and an organic light emitting device comprising the same.

The organic light emitting device is a device for converting electrical energy into light energy using an organic material, and includes an organic light emitting layer formed between the first electrode and the second electrode. The organic light emitting device may be formed in various structures, and among them, a tandem organic light emitting device in which a plurality of light emitting parts are stacked is being studied.

In the tandem organic light emitting device, an N-type charge generation layer and a P-type charge generation layer capable of generating electrons and holes between respective light emitting portions are formed. In general, charges are generated between the N-type charge generation layer and the P-type charge generation layer to transfer electrons to the electron injection layer adjacent to the N-type charge generation layer and to transfer holes to the hole injection layer adjacent to the P-type charge generation layer.

At this time, the larger the energy level difference between the N-type charge generation layer and the P-type charge generation layer, the more difficult electrons are injected into the N-type charge generation layer. In addition, when the alkali metal is doped into the N-type charge generation layer, the alkali metal may diffuse into an adjacent layer such as a P-type charge generation layer and current leakage may occur. This may lower the life of the device.

Korean Patent Publication No. 10-2013-0059328 (published 04 February 2013)

It is an object of the present invention to provide a phenanthroline-triazine compound of novel structure.

Another object of the present invention is to provide a phenanthroline-triazine compound which can improve the amount of electron injection in the light emitting part by minimizing the difference in energy level between the N-type charge generating layer and the P-type charge generating layer in a tandem organic light emitting diode and It is to provide an organic light emitting device comprising.

Still another object of the present invention is to provide a phenanthroline-triazine compound capable of minimizing the diffusion of alkali metal into the P-type charge generation layer, even when the N-type charge generation layer is doped with an alkali metal, and an organic compound including the same. It is to provide a light emitting device.

The object of the present invention is achieved by a phenanthroline-triazine compound represented by the following formula (1) or (2).

[Formula 1] [Formula 2]

In Formula 1 or 2, X ₁ , X ₂ , X ₃ and X ₄ are independently carbon or nitrogen, R ₁ to R ₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C1 to C60 straight or branched alkyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkenyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkynyl group; A substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; Substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; Substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group; -SiRR'R "; -P (= O) RR '; -S (= O) (= O) R and -NRR', and L is omitted or substituted or unsubstituted as follows: Phenylene or substituted or unsubstituted biphenylylene.

The phenanthroline-triazine compound can be selected from the compounds shown below.

 TRI

,

및

중 어느 하나이며, R은 각각 독립적으로, 생략될 수 있으며, 치환 또는 치환되지 않은 할로겐, 페닐, 알킬페닐, 비페닐, 알킬비페닐, 할로페닐, 알콕시페닐, 할로알콕시페닐, 시아노페닐, 실릴페닐, 나프틸, 알킬나프틸, 할로나프틸, 시아노나프틸, 실릴나프틸, 피리딜, 알킬피리딜, 할로피리딜, 시아노피리딜, 알콕시피리딜, 실릴피리딜, 피리미딜, 할로피리미딜, 시아노피리미딜, 알콕시피리미딜, 퀴놀리닐, 이소퀴놀리닐, 퀴녹살리닐, 피라지닐, 피리미딜, 퀴나졸리닐, 나프틸리디닐, 벤조티오페닐, 벤조퓨라닐, 디벤조티오페닐, 아릴티아졸릴, 디벤조퓨라닐, 플루오레닐, 카바조일, 이미다졸릴, 카볼리닐, 페난트레닐, 터페닐, 터피리디닐, 트리페닐레닐, 플루오르안테닐 및 디아카플루오레닐 중에서 선택될 수 있다.

,

And

Each independently, R may be omitted, substituted or unsubstituted halogen, phenyl, alkylphenyl, biphenyl, alkylbiphenyl, halophenyl, alkoxyphenyl, haloalkoxyphenyl, cyanophenyl, silyl Phenyl, naphthyl, alkylnaphthyl, halonaphthyl, cyanonaphthyl, silylnaphthyl, pyridyl, alkylpyridyl, halopyridyl, cyanopyridyl, alkoxypyridyl, silylpyridyl, pyrimidyl, halo Pyrimidyl, cyanopyrimidyl, alkoxypyrimidyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyrazinyl, pyrimidyl, quinazolinyl, naphthyridinyl, benzothiophenyl, benzofuranyl, dibenzothio Among phenyl, arylthiazolyl, dibenzofuranyl, fluorenyl, carbazoyl, imidazolyl, carbolinyl, phenanthrenyl, terphenyl, terpyridinyl, triphenylenyl, fluoroantenyl and diacafluorenyl Can be selected.

Another object of the present invention includes a first electrode, a second electrode and an organic material layer disposed between the first electrode and the second electrode to emit light, the organic material layer is composed of a plurality of layers, at least one The layer of is achieved by including a phenanthroline-triazine compound.

At least one organic material layer may include a charge generation layer (CGL).

The charge generation layer CGL may be N-type.

In the N-type charge generation layer, at least one of an alkali metal and an alkaline earth metal is doped to the phenanthroline-triazine compound, and the doped alkali metal is selected from Li, Na, K, Rb, and Cs. At least one, and the alkaline earth metal may be at least one of Be, Mg, Ca, Sr and Ba.

The organic material layer may include a first light emitting part, a second light emitting part positioned on the first light emitting part, and a first charge generating layer positioned between the first light emitting part and the second light emitting part.

 The organic material layer may further include a third light emitting part positioned on the second light emitting part, and a second charge generating layer positioned between the second light emitting part and the third light emitting part.

According to the present invention there is provided a phenanthroline-triazine compound of novel structure.

According to the present invention, a phenanthroline-triazine compound capable of improving the driving voltage and efficiency by improving an electron injection amount in a light emitting part by minimizing an energy level difference between an N-type charge generation layer and a P-type charge generation layer, and including the same An organic light emitting device is provided.

According to the present invention, even when the N-type charge generation layer is doped with an alkali metal, a phenanthroline-triazine compound capable of minimizing the diffusion of alkali metal into the P-type charge generation layer and an organic light emitting device comprising the same Is provided.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.
Figure 2 is a UV-PL curve measured the UV absorption and emission wavelength according to an embodiment of the present invention.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art to which the present invention pertains. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims.

The size and thickness of each component shown in the drawings are shown for convenience of description, and the present invention is not necessarily limited to the size and thickness of the illustrated configuration.

Each of the features of the various embodiments of the present invention may be combined or combined with each other in part or in whole, various technically interlocking and driving as can be understood by those skilled in the art, each of the embodiments may be implemented independently of each other It may be possible to implement the association together.

Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.

The phenanthroline-triazine compound according to the present invention is represented by the following general formula (1) or (2).

[Formula 1] [Formula 2]

In Formula 1 or 2, X ₁ , X ₂ , X ₃ and X ₄ are independently carbon or nitrogen, R ₁ to R ₇ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; A substituted or unsubstituted C1 to C60 straight or branched alkyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkenyl group; Substituted or unsubstituted C2 Through C60 A straight or branched chain alkynyl group; A substituted or unsubstituted C3 to C60 monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heterocycloalkyl group; Substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; Substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group; -SiRR'R "; -P (= O) RR '; -S (= O) (= O) R and -NRR', and L is omitted or substituted or unsubstituted as follows: Phenylene, or substituted or unsubstituted biphenylylene.

Substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described herein include both straight and pulverized forms.

'Aryl' described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes a system, including a form in which a plurality of aryl is connected by a single bond.

Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthasenyl, fluoranthenyl, and the like. It is not limited to this. Naphthyl can be 1-naphthyl and 2-naphthyl, anthryl can be 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl is 1-fluorenyl, 2-fluor Nil, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. 'Heteroaryl' described in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon. Meaning an aryl group which is 5 to 6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated.

In addition, the "heteroaryl" in the present invention also includes a form in which one or more heteroaryl is connected by a single bond. Such heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetra Monocyclic heteroaryl such as zolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothia Zolyl, Benzoisoxazolyl, Benzooxazolyl, Isoindoleyl, Indolyl, Indazolyl, Benzothiadiazolyl, Quinolyl, Isoquinolyl, Cinolinyl, Quinazolinyl, Quinoxalinyl, Carbazolyl, Phenantridinyl Polycyclic heteroaryls such as benzodioxolyl and the like, and their corresponding N-oxides (eg, pyridyl N-oxides, quinolyl N-oxides), quaternary salts thereof, and the like. .

In addition, the description of "substituted or unsubstituted" described in the present invention is that each of the substituents of R ₁ to R ₇ is independently (C1-C30) alkyl, (C6-C30) alkyl substituted or unsubstituted deuterium, halogen, halogen C30) aryl, (C6-C30) aryl substituted or unsubstituted (C3-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings , (C3-C30) cycloalkyl, (C6-C30) cycloalkyl fused with one or more aromatic rings, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri ( C6-C30) arylsilyl, adamantyl, (C7-C30) bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carbazolyl, NR ₂₁ R ₂₂ , BR ₂₃ R ₂₄ , PR ₂₅ R ₂₆ , P (= O) R ₂₇ R ₂₈ [R ₂₁ to R ₂₈ are independently of each other substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or Substituted or unsubstituted (C3-C30) heteroaryl.], (C6-C3) 0) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, (C1-C30) alkyloxy, (C1-C30) alkylthio, (C6-C30) aryloxy, (C6- C30) arylthio, (C1-C30) alkoxycarbonyl, (C1-C30) alkylcarbonyl, (C6-C30) arylcarbonyl, (C6-C30) aryloxycarbonyl, (C1-C30) alkoxycarbonyl At least one selected from the group consisting of oxy, (C1-C30) alkylcarbonyloxy, (C6-C30) arylcarbonyloxy, (C6-C30) aryloxycarbonyloxy, carboxyl, nitro or hydroxy More substituted or adjacent substituents are connected to form a ring.

The phenanthroline-triazine compound according to the present invention may be any one selected from the compounds shown below.

Here, TRI is

,

및

중 어느 하나일 수 있다.

,

And

It may be any one of.

Each R, independently, may be omitted, substituted or unsubstituted halogen, phenyl, alkylphenyl, biphenyl, alkylbiphenyl, halophenyl, alkoxyphenyl, haloalkoxyphenyl, cyanophenyl, silylphenyl, naphthyl, Alkyl naphthyl, halonaphthyl, cyanonaphthyl, silylnaphthyl, pyridyl, alkylpyridyl, halopyridyl, cyanopyridyl, alkoxypyridyl, silylpyridyl, pyrimidyl, halopyrimidyl, cyano Pyrimidyl, alkoxypyrimidyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyrazinyl, pyrimidyl, quinazolinyl, naphthyridinyl, benzothiophenyl, benzofuranyl, dibenzothiophenyl, arylthiazolyl , Dibenzofuranyl, fluorenyl, carbazoyl, imidazolyl, carbolinyl, phenanthrenyl, terphenyl, terpyridinyl, triphenylenyl, fluoroantenyl and diacafluorenyl.

In addition, the phenanthroline-triazine compound according to the present invention may be a compound represented by the following.

The compound represented by Chemical Formula 1 or Chemical Formula 2 described above may be schematically represented as follows.

In order to implement a high efficiency organic electroluminescent device, a material having an appropriate band gap and energy level must be developed. Materials with appropriate energy levels lower drive voltage and increase lifetime by facilitating charge injection into adjacent layers. In addition, the organic material used is thermally stable by having a high glass transition temperature (T _g ) and decomposition temperature (T _d ), thereby enabling continuous and stable operation of the device.

The compounds according to the invention comprise triazine cores which have a high charge mobility and are very thermally stable. The phenanthroline connected to the triazine core may combine with the metal doped in the charge generation layer to exhibit excellent N-type charge generation layer properties. As a result, a high efficiency organic light emitting diode can be realized.

More specifically, the phenanthroline core contains nitrogen (N) in the sp ² hybrid orbital, which is relatively rich in electrons, which binds to and gaps with alkali or alkaline earth metals, which are dopants of the N-type charge generation layer. A gap state is formed and the formed gap state facilitates the transfer of electrons from the N-type charge generation layer to the electron transport layer. By combining with a triazine core with high charge transport capacity, high electron affinity and thermal stability, the efficiency of charge transport can be maximized.

The linker regulates carrier mobility. It acts as a pathway to connect triazine and phenanthroline through regulation of conjugation, and it is possible to adjust the highest occupied molecular orbital (HOMO) and lower unoccupied molecular orbital (LUMO) values. Adjust

In particular, by adding a moiety having an N-type or P-type characteristic to a linker portion, fine bandgap tuning is possible. The compound according to the present invention, by adding an electron withdrawal moiety having a heteroaryl to relieve the strong electron attracting properties of phenanthroline and triazine, to disperse the electron density and to increase the chemical stability of the organic light emitting device It has the effect of improving the life of the.

In a stack structure, the material of the charge generating layer should not absorb light of the blue layer. The phenanthroline-triazine compound according to the present invention does not absorb light of the blue layer, and thus an efficient charge generation layer and a high efficiency organic light emitting device including the same can be realized.

The compound according to the present invention is excellent in thermal stability, the glass transition temperature is 128 ℃ or more, the melting temperature may be 296 ℃ or more. As a result, a high efficiency organic light emitting diode can be realized.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.

Referring to FIG. 1, the organic light emitting diode 1 has a tandem structure and includes a first electrode (anode 110), a second electrode (cathode 120), a first light emitter 210, and a second light emitter 220. The third light emitting unit 230 may include a first charge generation layer 240 and a second charge generation layer 250.

The first light emitter 210, the second light emitter 220, the third light emitter 230, the first charge generation layer 240, and the second 250 are organic layers and the first electrode 110 and the second light emitter. Located between the electrodes 120, the first charge generating layer 240 is located between the first light emitting portion 210 and the second light emitting portion 220, the second charge generating layer 250 is the second light emitting portion Located between the 220 and the third light emitting unit 230.

The first light emitting unit 210 includes a hole injection layer 211, a first hole transport layer 212, a first light emitting layer 213, and a first electron transport layer 214, and the second light emitting unit 220 is formed of a first light emitting layer 220. The second hole transport layer 221, the second light emitting layer 222 and the second electron transport layer 223, the third light emitting unit 230 is a third hole transport layer 231, the third light emitting layer 232, the third The electron transport layer 233 and the electron injection layer 234.

The first charge generation layer 240 is composed of an N-type charge generation layer 241 and a P-type charge generation layer 242, and the second charge generation layer 250 is an N-type charge generation layer 251 and a P-type. The charge generation layer 252. Each of the N-type charge generation layers 241 and 251 is doped with at least one of an alkali metal and an alkaline earth metal, and the doped alkali metal is doped with at least one of Li, Na, K, Rb, and Cs. The alkaline earth metal may be at least one of Be, Mg, Ca, Sr, and Ba.

The phenanthroline-triazine according to the present invention includes a first electron transport layer 214, a second electron transport layer 223, a third electron transport layer 233, an electron injection layer 234, and a first charge generation layer 240. And / or included in the second charge generation layer 250, and in particular, may be used in the N-type charge generation layers 241 and 251 and / or the electron transport layers 214, 223 and 233.

The organic light emitting device 1 described above can be variously modified. Some organic layers may be omitted or added, may not be tandem, or may be tandem with two or more light emitting layers. In addition, the organic light emitting device 1 may include an organic layer including a layer for simultaneously performing electron transport and electron injection. In this case, the phenanthroline-triazine compound according to the present invention may be used.

Hereinafter, Examples 1 to 6 and Comparative Examples of Compounds 1-1, 1-5, 1-9, 1-24, 1-25, 1-36, and an organic light emitting diode will be described. However, the production examples and examples described below are merely for illustrating or explaining the present invention in detail, and should not be construed as limiting the present invention by the production examples and examples described below.

[ Production Example ]

1.Intermediate (1): 2,4- diphenyl -6- (3- (4,4,5,5- tetramethyl Preparation of -1,3,2-dioxaborolan-2-yl) phenyl) -1,3,5-triazine

2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (20g, 51mmol) and Bis (pinacolato) diboron (27g, 61mmol), [1,1'-Bis (diphenyl phosphino) ferrocene ] Dioxane 260mL was added to dichloropalladium (II) (1.9g, 2.5mmol) and Potassium acetate (15.2g, 155mmol). After stirring for 17 hours at reflux, the mixture was cooled to room temperature. The reaction solution was filtered under reduced pressure through silica gel and celite to obtain a filtrate and concentrated. And recrystallized with dichloromethane and methanol, 21.5g (yield 96%) of intermediates (1) were obtained.

2. Intermediate (2): 1- (3,5- dibromophenyl ) of ethanone  Produce

1,3,5-tribromobenzene (20g, 64mmol) was dissolved in 500mL of Ether and cooled to -78 ℃. 39.6 mL 2.5 M n-Butyllithim was added slowly. After stirring at -78 ° C for 2 hours, 6.5 mL of N, N-dimethylacetamide dissolved in 50 mL of Ether was added slowly. Stir at room temperature for 17 hours. 350 mL of HCl (10%) was added to the reaction solution to terminate the reaction. After neutralizing the organic layer using dichloromethane and water, the water layer was removed, and the remaining water layer was removed using Magnesium sulfate. The organic layer was filtered under reduced pressure with silica gel and celite, and the filtrate was concentrated and recrystallized with ethanol to obtain 7.5 g (yield 43%) of intermediate (2).

3. Compound 1-1 Production Example

2- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (phenanthren-9-yl) phenyl) -1,10-phenanthroline represented by compound 1-1 is shown below. Prepared using the same reactions.

2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (16.5g, 35mmol) and phenanthren-9-ylboronic acid (5g, 24mmol), Tetrakis (triphenylphosphine) palladium (0) (1.4 g, 1.1 mmol) and Potassium carbonate (9.8 g, 71 mmol) were added to 150 mL of toluene, 150 mL of ethanol, and 150 mL of water, followed by stirring under reflux for about 5 hours. The resulting solids were obtained by filtration, dried twice after washing with water and once with methanol. 2- (3-bromo-5- (phenanthren-9-yl) phenyl) -4,6-diphenyl-1,3,5- after removing impurities through column separation (100% dichloromethane solution) 4g (30% yield) of triazine were obtained. Dioxane 100m in Bis (pinacolato) diboron (2.2g, 8.6mmol), [1,1′-Bis (diphenylphosphino) ferrocene] dichloropalladium (II) (0.26g, 0.36mmol), Potassium acetate (2.1g, 22mmol) Was added. After stirring for 17 hours at reflux, the mixture was cooled to room temperature. The reaction solution was filtered under reduced pressure with silica gel and celite to obtain a filtrate. 2-bromo-1,10-phenanthroline (1.5g, 5.8mmol), Tetrakis (triphenylphosphine) palladium (0) (0.3g, 0.26mmol) and Potassium carbonate (2.4g, 52mmol) were added to the filtrate for about 14 hours. Stirred under reflux. After cooling to room temperature, the organic layer was neutralized using dichloromethane and water, and then the water layer was removed, and the remaining water layer was removed using Magnesium sulfate. The organic layer was filtered under reduced pressure with silica gel and celite, and the crude obtained by performing silica gel adsorption column (eluent hexane: dichloromethane = 9: 1 → dichloromethane 100%) was washed with dichloromethane and hexane. 2g of compound 1-1 was obtained.

4. Of Compound 1-5 Production Example

2- (3- (dibenzo [b, d] furan-4-yl) -5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -1 represented by compound 1-5 , 10-phenanthroline was prepared using the following reactions.

2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (16.5g, 35mmol) and dibenzo [b, d] furan-4-ylboronic acid (5g, 24mmol), Tetrakis ( Triphenylphosphine) palladium (0) (1.4 g, 1.1 mmol) and Potassium carbonate (9.8 g, 71 mmol) were added to 120 mL of toluene, 120 mL of ethanol, and 120 mL of water, followed by stirring under reflux for about 3 hours. The resulting solid was obtained by filtration, dried three times after washing with water and two times with methanol. After removing impurities through column separation (100% of eluent hexane to 100% dichloromethane), 2- (3-bromo-5- (dibenzo [b, d] furan-4-yl) phenyl) -4, 4g (yield 30%) of 6-diphenyl-1,3,5-triazine was obtained. Dioxane 100m in Bis (pinacolato) diboron (2.2g, 8.6mmol), [1,1′-Bis (diphenylphosphino) ferrocene] dichloropalladium (II) (0.26g, 0.36mmol), Potassium acetate (2.1g, 22mmol) Was added. After stirring for 17 hours at reflux, the mixture was cooled to room temperature. The reaction solution was filtered under reduced pressure with silica gel and celite to obtain a filtrate. 2-bromo-1,10-phenanthroline (1.5g, 5.8mmol), Tetrakis (triphenylphosphine) palladium (0) (0.3g, 0.26mmol) and Potassium carbonate (2.4g, 17mmol) were added to the filtrate for about 14 hours. Stirred under reflux. After cooling to room temperature, proceed with a silica gel adsorption column (developing solution hexane: dichloromethane = 9: 1 → dichloromethane 100%) to wash the crude obtained with dichloromethane and hexane to obtain 1.5 g of compound 1-5. (50% yield) was obtained.

5. Of Compound 1-9 Production Example

2- (5- (4,6-diphenyl-1,3,5-triazin-2-yl) -4 '-(pyrimidin-2-yl)-[1,1'-biphenyl] represented by compound 1-9 -3-yl) -1,10-phenanthroline was prepared using the following reactions.

2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (19.8g, 42mmol) and (4- (pyrimidin-2-yl) phenyl) boronic acid (7g, 35mmol), Tetrakis (triphenylphosphine) palladium (0) (2.0 g, 1.8 mmol) and Potassium carbonate (14.5 g, 105 mmol) were added to 175 mL of toluene, 175 mL of ethanol, and 175 mL of water, followed by stirring under reflux for about 3 hours. The resulting solid was obtained by filtration, dried three times after washing with water and two times with methanol. After removing impurities through column separation (100% of eluent hexane → 100% dichloromethane), 2- (5-bromo-4 '-(pyrimidin-2-yl)-[1,1'-biphenyl]- 10 g (yield 53%) of 3-yl) -4,6-diphenyl-1,3,5-triazine was obtained. Dioxane 100m in Bis (pinacolato) diboron (5.6g, 22mmol), [1,1′-Bis (diphenylphosphino) ferrocene] dichloropalladium (II) (0.67g, 0.92mmol), Potassium acetate (5.4g, 55mmol) Input. After stirring for 17 hours at reflux, the mixture was cooled to room temperature. The reaction solution was filtered under reduced pressure with silica gel and celite to obtain a filtrate. 2-bromo-1,10-phenanthroline (4.4g, 17mmol), Tetrakis (triphenylphosphine) palladium (0) (1g, 0.85mmol) and Potassium carbonate (7g, 51mmol) were added to the filtrate and stirred under reflux for about 17 hours. did. After cooling to room temperature, a crude gel obtained by running a silica gel adsorption column (developing solution hexane: dichloromethane = 9: 1 to dichloromethane 100%) was recrystallized from dichloromethane and hexane to obtain 5 g of compound 1-9 ( Yield 50%).

6. Of Compound 1-24 Production Example

2- (2- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) pyridin-4-yl) -1,10-phenanthroline represented by compound 1-24 is shown below. Prepared using the reactions.

7. Of Compound 1-25 Production Example

2- (6- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) pyridin-2-yl) -1,10-phenanthroline represented by compound 1-25 is shown below. Prepared using the reactions.

8. Preparation of Compound 1-36

2- (3- (4,6-diphenyl-1,3,5-triazin-2-yl)-[1,1 ': 3', 1 ''-terphenyl] -5'- represented by compound 1-36 yl) -1,10-phenanthroline was prepared using the following reactions.

NMR data of the synthesized compounds are as follows.

compound 1 H NMR (CDCl 3) MS

Compound 1-1

1H δ
1 H NMR (500 MHz, CDCll 3) δ 9.69 (1H, s), 9.17 (1H, s), 9.04 (1H, s), 8.86-8.81 (7H, m), 8.43-8.39 (2H, d), 8.26- 8.24 (1H, m), 8.05-8.03 (2H, m), 7.97 (1H, s), 7.86-7.82 (2H, d), 7.74-7.55 (11H, m) 510.2
Compound 1-5

1H δ
1 H NMR (500 MHz, CDCl 3) δ 9.60 (1H, s), 9.53-9.53 (1H, m), 9.25-9.24 (1H, d), 9.17 (1H, m), 8.88-8.86 (4H, m), 8.44-8.37 (2H, dd), 8.28-8.26 (1H, m), 8.64-8.03 (2H, m), 7.97-7.95 (1H, m), 7.88-7.81 (2H, dd), 7.71-7.70 (1H , m), 7.67-7.53 (9H, m), 7.41-7.38 (1H, m) 654.2 Compound 1-9

1H δ
1 H NMR (500 MHz, CDCl 3) δ 9.56-9.55 (1H, t), 9.27-9.26 (1H, q), 9.19-9.18 (1H, t), 9.01-9.00 (1H, t), 8.88-8.85 (6H , m), 8.66-8.64 (2H, m), 8.47-8.45 (1H, d), 8.39-8.37 (1H, d), 8.30-8.28 (1H, q), 8.08-8.06 (2H, m), 7.90 -7.88 (1H, d), 7.85-7.83 (1H, d), 7.69-7.67 (1H, q), 7.365-7.60 (6H, m), 7.14-7.22 (1H, t) 642.2 Compound 1-24

1H δ
1 H NMR (500 MHz, CDCl 3) δ 9.58 (1H, s), 9.49-9.48 (1H, m), 9.29-9.28 (1H, m), 8.99-8.97 (1H, m), 8.89-8.87 (1H, d ), 8.85-8.83 (4H, m), 8.42-8.40 (2H, m), 8.31-8.29 (1H, d), 8.24-8.22 (1H, d), 8.15-8.13 (1H, d), 7.89-7.83 (2H, dd), 7.76-7.73 (1H, t), 7.70-7.68 (1H, m), 7.64-7.60 (6H, m) 565.2 Compound 1-25

1H δ
1 H NMR (500 MHz, CDCl 3) δ 9.21 (1H, m), 9.11 (1H, s), 8.82-8.79 (5H, m), 8.55-8.54 (2H, d), 8.39-8.37 (1H, d), 8.04-8.03 (2H, m), 7.86-7.80 (4H, m), 7.65-7.43 (9H, m) 565.2 Compound 1-36

1H δ
1 H NMR (500 MHz, CDCl 3) δ 9.21-9.20 (1H, m), 9.11 (1H, s), 8.82-8.79 (5H, m), 8.55-8.54 (2H, d), 8.39-8.37 (1H, d ), 8.27-8.23 (2H, m), 8.04-8.03 (2H, t), 7.86-7.80 (4H, m), 7.73-7.70 (1H, t), 7.65-7.51 (9H, m), 7.44-7.43 (1H, m) 640.2

[UV absorption wavelength spectrum measurement]

The UV / Vis absorption and emission wavelengths of the phenanthroline-triazine compound 1-1 according to the present invention were measured.

 Varian's Cary Eclipse was used as a fluorescence spectrophotometer, and the sample was measured by dissolving in methylene chloride at a concentration of 0.1-1 ppm.

UV-PL curve of Figure 2 shows the results of UV absorption and emission wavelength measurement of phenanthroline-triazine compound 1-1 according to the present invention. As shown in FIG. 2, it can be seen that the UV absorption wavelength of Compound 1-1 is within 400 nm and does not absorb light emitted from the blue layer.

[Glass Transition Temperature Measurement]

The glass transition temperature and melting temperature of Bphen mainly used in Preparation Examples 1 to 6 and the charge generation layer were measured and shown in Table 2 below.

division matter Tg ( ^o C) Tm ( ^o C) Comparative example BPhen 64 220 Preparation Example 1 Compound 1-1 168.16 318.30 Preparation Example 2 Compound 1-5 136.19 314.59 Preparation Example 3 Compound 1-9 144.76 291.24 Preparation Example 4 Compound 1-24 128.15 296.65 Preparation Example 5 Compound 1-25 129.23 314.90 Preparation Example 6 Compound 1-36 132.91 -

As shown in Table 2, Preparation Examples 1 to 6 it can be seen that the glass transition temperature and the melting temperature is much higher than the comparative example. Therefore, it can be confirmed that the compound according to the present invention has excellent thermal stability.

Hereinafter, an organic light emitting diode was manufactured and manufactured by using Bphen as a comparative example and compound 1-30 as an example in the charge generation layer.

[Production of Organic Light Emitting Device]

One. Comparative example  One

After the ITO substrate was patterned so that the light emitting area was 2 mm × 2 mm in size, washing was performed with isopropyl alcohol and UV ozone, respectively. Thereafter, the ITO substrate was mounted on the substrate holder of the vacuum deposition apparatus, and the pressure was set such that the vacuum degree was 1 × 10 ⁻⁷ torr.

First, a HAT-CN compound was vacuum deposited to form a 5 nm thick. This compound acts as a hole transport layer. An NPB material was formed to a thickness of 35 nm as a hole transport layer thereon.

Afterwards, a yellow light-emitting layer was formed by co-depositing a CPB material with a host and an Ir compound with a dopant at a thickness of 30 nm to have a mass ratio of about 10%.

An electron transport layer was formed on the light emitting layer with a TmPyPB compound having a thickness of 25 nm. Afterwards, a charge generation layer was formed by co-depositing the Li material on the BPhen material to a thickness of 10 nm to have a 2% mass ratio. Thereafter, Al was deposited to a thickness of 100 nm to form a cathode to fabricate an organic light emitting device.

2. EXAMPLE  One

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that only the charge generation layer material was changed to compound 1-1.

In the case of PIN OLEDs, low-voltage high-efficiency driving is realized through electrical doping of the charge transport layer in the OLED structure. The P doping layer is doped with an electron-lean organic material or metal oxide in the hole transport material, and the N doping layer is doped with an alkali metal such as lithium or cesium having a low work function in the electron transport material. The doped layer reduces the surface resistance of the organic material during operation to facilitate charge injection from adjacent layers. The introduction of a buffer layer on the doped anode layer realizes low voltage by energy banding and a low voltage driving technique using a material having high charge mobility.

Hereinafter, the current density, driving voltage, current efficiency, and external quantum efficiency of the organic light emitting diodes of Example 1 and Comparative Example 1 were measured and shown in Table 3 below.

matter J (mA / cm ² ) V cd / A lm / W QE Comparative Example 1 BPhen 10 4.5 56.5 39.4 19.1 Example 1 1-1 10 3.9 59.2 47.7 20

It can be seen that the driving voltage of Example 1 according to the present invention is lower than that of Comparative Example 1 while the current efficiency and external quantum efficiency of Example 1 are higher than that of Comparative Example.

3. Comparative example  2

After the ITO substrate was patterned so that the light emitting area was 2 mm × 2 mm in size, washing was performed with isopropyl alcohol and UV ozone, respectively. Thereafter, the ITO substrate was mounted on the substrate holder of the vacuum deposition apparatus and pressure was applied such that the vacuum degree was 1 × 10 ⁻⁷ torr.

First, a HAT-CN compound was vacuum deposited to form a 5 nm thick. This compound acts as the first hole injection layer. An NPB material was formed on the first hole transport layer to a thickness of 35 nm.

Thereafter, the CPB material was used as a host, and the Ir compound was co-deposited at a thickness of 30 nm to form a dopant of about 10% by mass to form a yellow first emission layer.

An electron transport layer was formed on the light emitting layer with a TmPyPB compound having a thickness of 25 nm. Afterwards, an N-type charge generation layer was formed by co-depositing a Li material on the BPhen material at a thickness of 10 nm to have a 2% mass ratio. Thereafter, a HAT-CN compound was vacuum deposited to a thickness of 5 nm with a P-type charge generation layer. Foreign substances are also used as the second hole injection layer. The NPB material was formed to a thickness of 35 nm as the second hole transport layer.

Afterwards, a second light emitting layer was formed by co-depositing a CPB material with a host and an Ir compound with a dopant to a thickness of about 30 nm at a thickness of 30 nm. A charge generating layer was formed on the light emitting layer with a TmPyPB compound having a thickness of 25 nm. The LiF material was then vacuum deposited to a thickness of 1 nm into the electron injection layer. Finally, Al was deposited to a thickness of 100 nm to form a cathode to fabricate an organic EL device.

4. EXAMPLE  2

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the organic material of the N-type charge generation layer with compound 1-5.

5. EXAMPLE  3

The organic light emitting device was fabricated in the same manner as in the comparative example above, but replacing only the organic material of the N-type charge generation layer with compound 1-9.

6. EXAMPLE  4

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the organic material of the N-type charge generation layer with compound 1-24.

7. EXAMPLE  5

The organic light emitting device was fabricated in the same manner as the comparative example described above, except that only the organic material of the N-type charge generation layer was changed to compound 1-25.

8. EXAMPLE  6

The organic light emitting device was manufactured by the same method as the comparative example described above, but replacing only the organic material of the N-type charge generation layer with compound 1-36.

The tandem structure is a structure in which EL units including a doped hole transport layer and an electron transport layer are vertically stacked, and current luminous efficiency increases in proportion to the number of stacked layers. In this case, the CGL (change generation layer) layer is a concept of a transparent PN junction, and can be understood as a concept in which a unit PIN OLED light emitting unit is stacked in a plurality of layers. Therefore, the efficiency and voltage of the stack structure can be predicted by the single-layer PIN OLED embodiment, and the efficiency and voltage of the three-layer structure can be predicted by the two-layer structure.

The current density, driving voltage, current efficiency, and external quantum efficiency of the organic light emitting diodes of Examples 2 to 6 and Comparative Example 2 were measured and shown in Table 4.

division matter Drive current J (mA / cm2) Drive Voltage Current efficiency
(cd / A) Luminous Efficiency (lm / W) EQE (%) Comparative Example 2 BPhen 10 9.4 107.8 36.0 35 Example 2 1-5 10 8.71 123 44.4 39.1 Example 3 1-9 10 8.61 126.5 46.2 40.0 Example 4 1-24 10 8.7 125.5 45.3 39.9 Example 5 1-25 10 8.44 121.8 45.3 37.5 Example 6 1-36 10 8.66 129.5 47.0 40.0

As shown in Table 4, in Examples 2 to 6, the driving voltage (V) was lowered compared to Comparative Example 2, while the current efficiency (cd / A) and external quantum efficiency (QE) were lowered. It can be seen that it is excellent.

Therefore, it can be seen that the organic light emitting device including the phenanthroline-triazine compound according to the present invention has improved lifespan and improved efficiency compared to the organic light emitting device including the conventional compound.

The present invention is not necessarily limited to these embodiments, and various modifications can be made without departing from the spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (9)

A phenanthroline (triazine) compound, characterized in that any one selected from the compounds shown below.

delete delete A first electrode;
Second electrode; And
An organic material layer disposed between the first electrode and the second electrode and emitting light;
The organic layer is composed of a plurality of layers, at least one layer of the organic light emitting device comprising the phenanthroline-triazine compound according to claim 1. The method of claim 4, wherein
The at least one organic material layer is an organic light emitting device, characterized in that it comprises a charge generation layer (CGL). The method of claim 5,
The charge generation layer (CGL) is an organic light emitting device, characterized in that the N-type. The method of claim 6,
The N-type charge generation layer,
At least one of an alkali metal and an alkaline earth metal is doped to the phenanthroline-triazine compound,
The doped alkali metal is at least one of Li, Na, K, Rb and Cs,
The alkaline earth metal is at least any one of Be, Mg, Ca, Sr and Ba. The method of claim 4, wherein
The organic material layer,
A first light emitting unit;
A second light emitting unit positioned on the first light emitting unit; and
A first charge generation layer positioned between the first light emitting unit and the second light emitting unit;
An organic light emitting device comprising a. The method of claim 8,
The organic material layer,
A third light emitting unit positioned on the second light emitting unit;
A second charge generation layer positioned between the second light emitting part and the third light emitting part;
An organic light emitting device characterized in that it further comprises.

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