KR20160121628A - Organic material and oled having the same - Google Patents

Abstract

The present invention relates to an organic material and an organic light-emitting diode comprising the same. The organic material can be represented as chemical formula 1. In the chemical formula 1, R_1 and R_2 can be independently an aryl group having 5-30 carbon atoms or an alkylaryl group having 5-30 carbon atoms respectively, and R_1 and R_2 are not fused or are fused with each other to form a saturated or unsaturated ring with an attached nitrogen. N can be an integer of 2 or 3, and R_3-R_12 can be independently a hydrogen, a heavy hydrogen, an alkyl group having 5-30 carbon atoms, or NR_13R_14. R_13 and R_14 can be independently an aryl group having 5-30 carbon atoms, or an alkyl group having 5-30 carbon atoms, and R_13 and R_14 are not fused or are fused with each other to form a saturated or unsaturated ring with an attached nitrogen.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic material and an organic light-

TECHNICAL FIELD The present invention relates to a compound for an organic light emitting diode, and more particularly to a retarded fluorescent light emitting material.

An organic light emitting diode (OLED) is a self-luminous type device having a wide viewing angle, excellent contrast, fast response time, excellent luminance, driving voltage and response speed characteristics, and multi-coloring.

A typical organic light emitting diode may include an anode and a cathode and an organic layer interposed between the anode and the cathode. The organic layer may include an electron injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light emitting layer via the hole transporting layer, and electrons injected from the cathode move to the light emitting layer via the electron transporting layer. Carriers such as holes and electrons recombine in the light emitting layer region to generate an exiton, which is converted to a base state and light is generated.

To solve this problem, recently retarded fluorescent light emitting materials have been developed. The retarded fluorescent light emitting material has a difference in singlet state and triplet state of excitons of 0.3 eV or less. In this case, the triplet state is converted into a singlet state by heat corresponding to room temperature or device driving temperature, And the quantum efficiency of the quantum efficiency is reported.

However, the currently developed delayed fluorescent light emitting material needs to further improve its actual efficiency, and it is necessary to improve the lifetime.

An object of the present invention is to provide an organic material having improved efficiency and improved lifetime and an organic light emitting diode containing the organic material.

According to one aspect of the present invention, there is provided an organic material for an organic light emitting diode. The organic material may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ may each independently be a C5 to C30 aryl group or a C5 to C30 alkylaryl group. R ₁ and R ₂ may not be fused to each other or may fuse together with the nitrogen to which they are attached to form a saturated or unsaturated ring.

n may be an integer of 2 or 3. R ₃ to R ₁₂ each independently may be hydrogen, deuterium, a C 1 to C 30 alkyl group, or NR ₁₃ R ₁₄ . R ₁₃ and R ₁₄ are each independently a C5 to the aryl group of the C30, or C5 to may be an alkyl aryl of C30, R ₁₃ and R ₁₄ are either not fused together or fused to a saturated or unsaturated, with which they are attached nitrogen A ring can be formed.

The organic material may be a retarded fluorescent light emitting material.

NR ₁ R ₂ and NR ₁₃ R ₁₄ may be the following functional groups regardless of each other.

In the functional group 1, the functional group 2, or the functional group 3, A ₁ and A ₂ may be hydrogen, deuterium, or a C1 to C4 alkyl group, regardless of each other.

The organic material represented by Formula 1 may be an organic material represented by Formula 2 below.

(2)

In Formula 2, R _1a , R _2a , R _1b , and R _2b are each independently a C5 to C30 aryl group, or a C5 to C30 alkylaryl group. R _{< 1a >} and R < _2a > may not be fused to each other, or may fuse together with the nitrogen to which they are attached to form a saturated or unsaturated ring. R _1b and R _2b may not be fused to each other, or may fuse together with the nitrogen to which they are attached to form a saturated or unsaturated ring. R ₃ to R ₁₂ may be the same as defined in formula (1).

The organic material represented by the formula (2) may be the following compound 4 or 5.

.

The organic material represented by Formula 1 may be an organic material represented by Formula 3 below.

(3)

In Formula 3, R _1a , R _2a , R _1b , R _2b , R _1c , and R _2c are each independently a C5 to C30 aryl group or a C5 to C30 alkylaryl group. R _{< 1a >} and R < _2a > may not be fused to each other, or may fuse together with the nitrogen to which they are attached to form a saturated or unsaturated ring. R _1b and R _2b may not be fused to each other, or may fuse together with the nitrogen to which they are attached to form a saturated or unsaturated ring. R _1c and R _2c may not be fused to each other or may fuse together with the nitrogen to which they are attached to form a saturated or unsaturated ring. R ₃ to R ₁₂ may be the same as defined in formula (1).

The organic material represented by Formula 3 may be Compound 1, Compound 2, Compound 3, Compound 6 or Compound 7 shown below.

According to one aspect of the present invention, there is provided an organic light emitting diode. The organic light emitting diode includes an anode, a hole conduction layer, a light emitting layer, an electron conduction layer, and a cathode sequentially stacked, wherein any one of the hole conduction layer, the light emitting layer, and the electron conduction layer includes the organic material of claim 1.

The light emitting layer may include a host material and a dopant material, and the dopant material may include the organic material of claim 1.

According to the embodiments of the present invention, two or more donor units such as NR ₁ R ₂ are connected to the benzene ring represented by the formula (1), and triazine, which is an acceptor unit having excellent structural stability, is connected to the benzene ring , Electron-accepting structures are formed in the molecular structure, and charge transfer complex forms are formed in the molecular structure, so that the singlet energy and the triplet energy difference, that is, the narrow △ Est, may appear. Therefore, the organic material can realize delayed fluorescence and improve the quantum efficiency and lifetime of the organic light emitting diode.

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

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals designate like elements throughout the specification.

As used herein, unless otherwise defined, the term "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds. The alkyl group may be an "unsaturated alkyl group" comprising at least one double bond or triple bond. The alkyl group, whether saturated or unsaturated, can be branched, straight chain or cyclic. For example, the C1 to C4 alkyl group may be selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl.

As used herein, the term "aryl group" means a polycyclic aromatic compound composed of a monocyclic aromatic compound or a fused aromatic ring unless otherwise defined, and includes a heteroaryl group.

The term "heteroaryl group ", as used herein, unless otherwise defined, includes at least one heteroatom selected from the group consisting of N, O, S, Se, and P in at least one ring, Means a polycyclic aromatic compound consisting of a phosphorus, monocyclic aromatic compound or fused aromatic rings.

In the present specification, when "Cx to Cy" is described, it is to be interpreted that the number of carbon atoms corresponding to all integers between the number of carbon atoms x and the number of carbon atoms y is also described.

Organic material

The following Formula 1 represents an organic material according to an embodiment of the present invention.

In Formula 1,

R ₁ and R ₂ are each independently a C5 to C30 aryl group or a C5 to C30 alkylaryl group and R ₁ and R ₂ are not fused to each other or fused to form a saturated or unsaturated ring together with the nitrogen to which they are attached Lt; / RTI >

n may be an integer of 2 or 3,

R ₃ to R ₁₂ each independently may be hydrogen, deuterium, a C 1 to C 30 alkyl group, or NR ₁₃ R ₁₄ . R ₁₃ and R ₁₄ are each independently a C5 to the aryl group of the C30, or C5 to may be an alkyl aryl of C30, R ₁₃ and R ₁₄ is a saturated or unsaturated ring together with the nitrogen to which they are attached to, or not fused together or fused Can be formed.

Such an organic material may be an organic material for an organic light emitting diode and may be used for any one of the organic layers of the organic light emitting diode. Specifically, the organic material may be any one of a hole conduction layer, a light emitting layer, and an electron conduction layer, more specifically, a hole injecting material, a hole transporting material, an exciton blocking material, a light emitting host material, a light emitting dopant material, Or an electron transporting material. Specifically, the organic material can be used as a luminescent dopant material.

Also, since the organic material has two or more donor units such as NR ₁ R ₂ connected to the benzene ring, and triazine, which is an exocenter unit having excellent structural stability, is connected to the benzene ring, the electron- And a charge transfer complex form is formed in the molecular structure, so that a singlet energy and a triplet energy difference, that is, a narrow △ Est, may appear. Therefore, the organic material can realize delayed fluorescence and improve the quantum efficiency and lifetime of the organic light emitting diode.

In the above formula (1), NR ₁ R ₂ or NR ₁₃ R ₁₄ may be the following functional groups regardless of each other.

In the functional group 1, the functional group 2, or the functional group 3, A ₁ and A ₂ may be hydrogen, deuterium, or a C1 to C4 alkyl group, regardless of each other.

The following formulas (2) and (3) represent organic materials according to one embodiment of the present invention.

In the general formula 2 or general formula _{3, R 1a, R 2a,} R 1b, R 2b, R 1c, and R _2c are each independently selected from C5 to the aryl group of the C30, or C5 to may be an alkyl aryl of C30, R _1a And R < _2a > may not be fused or fused to form a saturated or unsaturated ring together with the nitrogen to which they are attached, and R _{< 1b} > and R < _{2b >} are not fused to each other or fused to form a saturated or unsaturated ring And R _1c and R _2c may not fuse with each other or may fuse together with the nitrogen to which they are attached to form a saturated or unsaturated ring,

R ₃ to R ₁₂ may be the same as defined in formula (1).

In the general formula (2) or (3), NR _1a R _2a , NR _1b R _2b , and NR _1c R _2c may each independently be the functional group 1 or the functional group 2.

In the above formulas 1 to 3, R ₉ and R ₁₁ may each independently be the functional group 1 or the functional group 2. In this case, R ₃ to R ₈ , R ₁₀ , and R ₁₂ may be hydrogen.

  The following compounds 1-7 represent organic materials according to one embodiment of the present invention.

Organic light emitting diode

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

1, an organic light emitting diode includes an anode 10 and a cathode 70, a light emitting layer 40 disposed between the two electrodes, a hole conduction layer 20 disposed between the anode 10 and the light emitting layer 40, And an electron conduction layer 50 disposed between the light emitting layer 40 and the cathode 70. The hole transport layer 20 may include a hole transport layer 25 for transporting holes and a hole injection layer 23 for facilitating injection of holes. In addition, the electron conduction layer 50 may include an electron transport layer 55 for transporting electrons and an electron injection layer 53 for facilitating injection of electrons. In addition, a first exciton blocking layer (not shown) may be disposed between the light emitting layer 40 and the hole transport layer 25. A second exciton blocking layer (not shown) may be disposed between the light emitting layer 40 and the electron transporting layer 55. Alternatively, however, the present invention is not limited to this, and the electron transport layer 55 may serve as a second exciton blocking layer, or the hole transport layer 25 may serve as a first electron blocking layer.

When a forward bias is applied to the organic light emitting diode, holes are injected from the anode 10 into the light emitting layer 40, and electrons from the cathode 70 are injected into the light emitting layer 40. Electrons and holes injected into the light emitting layer 40 are combined with each other to form excitons, and light is emitted while the excitons transition to the ground state.

The light emitting layer 40 may be made of a single light emitting material, and may include a light emitting host material and a light emitting dopant material. When the light emitting layer 40 includes a light emitting host material and a light emitting dopant material, the electrons and holes injected into the light emitting layer 40 are combined at the light emitting host material to form an exciton, and then the exciton is transferred to the light emitting dopant material, Lt; / RTI > The light emitting layer 40 including the light emitting host material and the light emitting dopant material may be a phosphorescent light emitting layer or a fluorescent light emitting layer, for example, a delayed fluorescent light emitting layer.

Any one of the organic materials of the formulas 1 to 3 and the compounds 1 to 7 may be used in any one of the organic layers 20, 40, and 50 of the organic light emitting diode. Specifically, the organic materials of the above-mentioned Formulas 1 to 3 and the compounds 1 to 7 may be any of a hole injecting material, a hole transporting material, an exciton blocking material, a light emitting host material, a light emitting dopant material, an electron injecting material, Can be used as one. Specifically, the organic material may be used as a light emitting dopant material, and in this case, the light emitting layer 40 may be a delayed fluorescent light emitting layer.

Also, since the organic material has two or more donor units such as NR ₁ R ₂ connected to the benzene ring, and triazine, which is an exocenter unit having excellent structural stability, is connected to the benzene ring, the electron- And a charge transfer complex form is formed in the molecular structure, so that a singlet energy and a triplet energy difference, that is, a narrow △ Est, may appear. Therefore, the organic material can improve quantum efficiency and lifetime of the organic light emitting diode.

The host of the light emitting layer 40 may be selected from mCP (N, N-dicarbazolyl-3,5-benzene), diphenylphosphine oxide-4- (triphenylsilyl) phenyl, DPEPO, bis [2- (diphenylphosphino) ), BSCP (4,4'-bistriphenylsilanyl-biphenyl), UGH3 (m-bis- (triphenylsilyl) benzene), SimCP (3,5-di (N-carbazolyl) tetraphenylsilane) (9H-carbazol-9-yl) phenyl) diphenylsilane), CzSi (9- (4- tertbutylphenyl) -3,6-bis (triphenylsilyl) ) silane), DCPPO ((3,5-di (9H-carbazole-9-yl) phenyl) diphenylphosphine oxide), DFCz (2,8-di ), DBT1 (2,8-di (9H-carbazol-9-yl) dibenzo [b, d] thiophene, 26mCPy have. In addition, the host may be selected from the group consisting of Alq3, CBP (4,4'-N, N'-dicarbazole-biphenyl), 9,10-di (naphthalen- N-phenylbenzimidazole-2-yl benzene), TBADN (3-tert-butyl-9,10-di (naphtho- 2-yl) anthracene), E3 (see the following formula), or BeBq2 (see the following formula).

The anode 10 may be a conductive metal oxide, a metal, a metal alloy, or a carbon material. The conductive metal oxide is indium tin oxide (indium tin oxide: ITO), fluorine tin oxide (fluorine tin oxide: FTO), antimony tin oxide (antimony tin oxide, ATO), fluorine-doped tin oxide (FTO), SnO _2, ZnO , Or a combination thereof. The metal or metal alloy suitable as the anode 10 may be Au and CuI. The carbon material may be graphite, graphene, or carbon nanotubes.

The hole injection layer 23 and / or the hole transport layer 25 are layers having a HOMO level between the work function level of the anode 10 and the HOMO level of the light emitting layer 40, The hole injection or transport efficiency of the hole is enhanced. The electron injection layer 53 and / or the electron transport layer 55 are layers having a LUMO level between the work function level of the cathode 70 and the LUMO level of the light emitting layer 40, ) In order to increase the injection or transport efficiency of electrons.

The hole injecting layer 23 or the hole transporting layer 25 may include a material commonly used as a hole transporting material and one layer may have a different hole transporting material layer. The hole-transporting material may be, for example, mCP (N, N-dicarbazolyl-3,5-benzene); PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrenesulfonate); NPD (N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine); N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPD); N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl; N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl; N, N, N'N'-tetraphenyl-4,4'-diaminobiphenyl; Porphyrin compound derivatives such as copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin and the like; TAPC (1,1-Bis [4- [N, N'-Di (p-tolyl) Amino] Phenyl] cyclohexane; Triarylamine derivatives such as N, N, N-tri (p-tolyl) amine and 4,4 ', 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine; Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; Phthalocyanine derivatives such as nonmetal phthalocyanine and copper phthalocyanine; Starburst amine derivatives; Enamnstilbene derivatives; Derivatives of aromatic tertiary amines and styryl amine compounds; And polysilane. The hole transporting material may serve as a first exciton blocking layer.

The second exciton blocking layer serves to prevent the triplet excitons or holes from diffusing toward the cathode 70, and may be selected arbitrarily from known hole blocking materials. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and the like can be used.

The electron transporting layer 55 may be formed of at least one selected from the group consisting of diphenylphosphine oxide-4- (triphenylsilyl) phenyl, TPBi (1,3,5-tris (N-phenylbenzimidazol- ), Aluminum (Alq3), 2,5-diarylsilole derivative (PyPySPyPy), perfluorinated compound (PF-6P), COTs (Octasubstituted cyclooctatetraene), TAZ (4,7-diphenyl-1,10-phenanthroline), BCP (see the following chemical formula), or Balq (see the following chemical formula).

The electron injection layer 53 may be, for example, LiF, NaCl, CsF, Li2O, BaO, BaF2, or Liq (lithium quinolate).

The cathode 70 is a conductive film having a lower work function than the anode 70 and is made of a metal such as aluminum, magnesium, calcium, sodium, potassium, indium, yttrium, lithium, May be formed using a combination of two or more of them.

The anode 10 and the cathode 70 may be formed using a sputtering method, a vapor deposition method, or an ion beam deposition method. The hole injecting layer 23, the hole transporting layer 25, the light emitting layer 40, the hole blocking layer, the electron transporting layer 55 and the electron injecting layer 53 are formed by a vapor deposition method or a coating method, , Spin coating, dipping, printing, doctor blading, or electrophoresis.

The organic light emitting diode may be disposed on a substrate (not shown), which may be disposed under the anode 10 or above the cathode 70. In other words, the anode 10 may be formed on the substrate before the cathode 70, or the cathode 70 may be formed before the anode 10.

The substrate may be a light-transmissive substrate as a flat plate member, in which case the substrate may be glass; Ceramics material; And may be made of a polymer material such as polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polypropylene (PP) However, the present invention is not limited to this, and the substrate may be a metal substrate capable of light reflection.

Hereinafter, exemplary embodiments of the present invention will be described in order to facilitate understanding of the present invention. It should be understood, however, that the following examples are intended to aid in the understanding of the present invention and are not intended to limit the scope of the present invention.

[Experimental Examples; Examples]

Intermediate Synthesis Example 1: Intermediate 1

[Reaction Scheme 1]

(10.65 g, 39.80 mmol), (3,4,5-trifluorophenyl) boronic acid (7.00 g, 39.80 mmol) was added to a solution of 2- Dissolved in 210 ml of tetrahydrofuran and dissolved by stirring in a nitrogen stream. Potassium carbonate (16.50 g, 119.39 mmol) was dissolved in distilled water (70 ml) and added to the above reaction solution. Tetrakis (triphenylphosphine) palladium (0) (2.30 g, 2.00 mmol) was added thereto, and the mixture was heated to reflux and stirred. After 12 hours, the temperature of the reactant was lowered to room temperature and the precipitate was filtered. The filtered solid was washed with EA (ethylacetate) to give 12.50 g of pure white solid intermediate 1 in 86% yield.

Intermediate Synthesis Example 2: Intermediate 2

[Reaction Scheme 2]

9 H -carbazole (0.22 g, 1.32 mmol) was dissolved in 10 ml of tetrahydrofuran and slowly added to a flask under a stream of nitrogen containing sodium hydride (0.05 g, 2.20 mmol). After stirring for 30 minutes, Intermediate 1 (0.40 g, 1.10 mmol) was dissolved in 10 ml of tetrahydrofuran and added to the above flask. The temperature of the reaction mixture was raised, and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The resulting solid material was washed with distilled water and then backwashed with EA. Finally, recrystallization on toluene afforded 0.35 g of pure white solid intermediate 2 in 62% yield.

Intermediate Synthesis Example 3: Intermediate 3

[Reaction Scheme 3]

3,6-dimethyl -9 H - a carbazole (1.61 g, 8.26 mmol) was slowly added to sodium hydride (0.40 g, 16.51 mmol) the flask under a nitrogen gas stream containing dissolved in 50 ml of tetrahydrofuran. After stirring for 30 minutes, Intermediate 1 (3.00 g, 8.26 mmol) was dissolved in 30 ml of tetrahydrofuran and introduced into the above flask. The temperature of the reaction mixture was raised, and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The resulting solid material was washed with distilled water and then backwashed with EA. Finally, recrystallization on toluene afforded 3.60 g of pure, light yellow solid intermediate 3 in 81% yield.

Compound Synthesis Example 1: Compound 1

[Reaction Scheme 4]

9 H -carbazole (0.55 g, 3.30 mmol) was dissolved in 10 ml of dimethylformamide and slowly added to a flask under a stream of nitrogen containing sodium hydride (0.09 g, 3.72 mmol). After stirring for 30 minutes, Intermediate 1 (0.30 g, 0.83 mmol) was dissolved in 10 ml of dimethylformamide and introduced into the above flask. The temperature of the reaction mixture was raised, and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The resulting solid material was washed with distilled water and then backwashed with EA. Subsequently, sublimation purification was carried out to obtain 0.48 g of a pure greenish yellow solid compound 1 in 72% yield.

Compound 1 : Mass spectrometry (FAB) m / z 804 [(M + H) <^+> ]. ^{1 H NMR (400 MHz, DMSO} ): δ6.68 (t, 2H, J = 8.2Hz), 6.78 (t, 2H, J = 7.0Hz), 7.05 ~ 7.08 (m, 8H), 7.25 (d, 2H J = 8.4 Hz), 7.43-7.49 (m, 6H), 7.56 (t, 4H, J = 7.8Hz), 7.65 (d, 4H, J = 8.8 Hz), 9.18 (s, 2H)

Compound Synthesis Example 2: Compound 2

[Reaction Scheme 5]

3,6-dimethyl -9 H - carbazole (0.71 g, 3.63 mmol) was slowly added to sodium hydride (0.13 g, 5.50 mmol) the flask under a nitrogen gas stream containing dissolved in 10 ml of dimethylformamide. After stirring for 30 minutes, Intermediate 1 (0.40 g, 1.10 mmol) was dissolved in 10 ml of dimethylformamide and introduced into the above flask. The temperature of the reaction mixture was raised, and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The resulting solid material was washed with distilled water and then backwashed with EA. Subsequently, sublimation purification was carried out to obtain 0.83 g of a pure yellow solid compound 2 in a yield of 85%.

Compound 2 : Mass Spec (FAB) m / z 888 [(M + H) &lt; ⁺ & gt ^; ]. ^{1 H NMR (400 MHz, CDCl} 3): δ 2.18 (s, 6H), 2.38 (s, 12H), 6.48 (d, 2H, J = 9.6Hz), 6.85 (t, 6H, J = 6.6Hz), 2H, J = 8.8 Hz), 9.12 (s, 2H), 7.12 (d, 6H, J = 8.4 Hz), 7.49-7.59

Compound Synthesis Example 3: Compound 3

[Reaction Scheme 6]

9,9-Dimethyl-9,10-dihydroacridine (0.89 g, 4.24 mmol) was dissolved in 15 ml of dimethylformamide and slowly added to a flask under a stream of nitrogen containing sodium hydride (0.16 g, 6.74 mmol) Respectively. After stirring for 30 minutes, intermediate 2 (0.70 g, 1.93 mmol) was dissolved in 15 ml of dimethylformamide and introduced into the above flask. The temperature of the reaction mixture was raised, and the mixture was refluxed for 8 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The resulting solid material was washed with distilled water and then backwashed with EA. Finally, sublimation purification was carried out to obtain 0.28 g of a pure yellow solid compound 3 in a yield of 16%.

Compound 3 : Mass spectrometry (FAB) m / z 888 [(M + H) &lt; ⁺ & gt ^; ]. ^{1 H NMR (400 MHz, CDCl} 3): δ-0.16 (s, 6H), 1.60 (s, 6H), 6.64 (t, 2H, J = 7.2Hz), 6.71 (d, 2H, J = 7.6Hz) , 6.77 (d, 4H, J = 9.2 Hz), 7.04 (t, 4H, J = 8.6 Hz), 7.17 (d, 4H, J = 9.2 Hz), 7.52-7.61 (m, 8H)

Synthesis Example 4: Intermediate 4 (9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole)

10 g of 1,3,5-tribromobenzene, 11.95 g of 9H-carbazole, 9.87 g of potassium carbonate and 1.29 g of 1,10-petatroline were dissolved in 120 ml of dimethylformamide, and then cooper ion And the mixture was refluxed at a temperature of 180 ° C or more for 12 hours. After the temperature was lowered to room temperature, distilled water was poured to terminate the reaction, and the reaction was terminated. The reaction mixture was extracted with methylene chloride, and the solvent was dried and purified by column chromatography (MC: HEX). As a result, Intermediate 4 (9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole)) was obtained (6 g).

Intermediate 5 Synthesis of Intermediate 5 (9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan-2-yl) Bis (9H-carbazole)

(Intermediate 3), 1.89 g of bispinacolatodiaboron, 1.69 g of potassium acetate, 1.9 g of 1,1'- (5-bromo-1,3-phenylene) 0.14 g of bis [(diphenylphosphino) ferrocene] dichloropalladium (II) was dried in vacuum and dissolved in 60 ml of 1,4-dioxane. The mixture was maintained under a nitrogen atmosphere for 30 minutes, Respectively. After the temperature was lowered to room temperature, distilled water was poured to terminate the reaction, and the reaction was terminated. The reaction mixture was extracted with methylene chloride, and the solvent was dried and purified by column chromatography (MC: HEX). As a result, a solution of Intermediate 5 (9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaballol-2-yl) Carbazole)) (2.3 g was obtained).

Compound Synthesis Example 4: Compound 4 (9,9 '- (5- (4,6-diphenyl-1,3,5-triazine-2-yl) Sol))

[Reaction Scheme 7]

9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaballol-2-yl) -1,3-phenylene) bis (9H- carbazole) 1.55 0.6 g of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.16 g of tetrakis (triphenylphosphine) palladium (0), 10 ml of a 2 mol potassium carbonate aqueous solution, 20 ml of tetrahydrofuran was refluxed at a temperature of 100 DEG C or higher for 2 hours. After the temperature was lowered to room temperature, the reaction was terminated. The extracted powder was filtered, washed with water, methylene chloride, and hexane, and purified. Finally, sublimation purification was performed to obtain 1.3 g of a greenish compound 4 in 91% yield.

Compound 4 : mass spectrometry (FAB) m / z 639 [(M + H) &lt; ⁺ & gt ^; ]. ^{1 H NMR (400 MHz, CDCl} 3): δ9.11 (s, 2H), 8.74 (d, 4H, J = 8.4Hz), 8.21 (d, 4H, J = 8.0Hz), 8.05 (s, 1H) , 7.64-7.47 (m, 14H), 7.36 (t, 4H, J = 16.0 Hz).

Compound Synthesis Example 5: Compound 5 (9,9 '- (5- (4,6-diphenyl-1,3,5-triazine-2-yl) Sol))

[Reaction Scheme 8]

9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaballol-2-yl) -1,3- phenylene) bis (9H- carbazole) 1.63 0.3 g of 2,4-dichloro-6-phenyl-1,3,5-triazine, 0.09 g of tetrakis (triphenylphosphine) palladium (0), 10 ml of a 2 mol potassium carbonate aqueous solution, 30 ml of tetrahydrofuran was refluxed at a temperature of 100 DEG C or higher for 2 hours. After the temperature was lowered to room temperature, the reaction was terminated. The extracted powder was filtered, washed with water, methylene chloride, and hexane, and purified. Finally, sublimation purification was performed to obtain 1.1 g of 85% of compound 5 in white light.

Compound 5 : mass spectrometry (FAB) m / z 971 [(M + H) <^+> ]. ^{1 H NMR (400 MHz, CDCl} 3): δ9.04 (s, 4H), 8.69 (d, 2H, J = 7.6Hz), 8.16 (d, 7H, J = 7.2Hz), 8.05 (m, 2H) , 7.59 (d, 9H, J = 7.6Hz), 7.52-7.48 (m, 2H), 7.37-7.28 (m, 17H).

Compound Synthesis Example 6: Compound 6

[Reaction Scheme 9]

9 H -carbazole (0.58 g, 3.44 mmol) was dissolved in 10 ml of dimethylformamide and slowly added to a flask under a stream of nitrogen containing sodium hydride (0.10 g, 4.13 mmol). After stirring for 30 minutes, Intermediate 3 (0.50 g, 1.38 mmol) was dissolved in 10 ml of dimethylformamide and added to the above flask. The temperature of the reaction mixture was raised, and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The resulting solid material was washed with distilled water and then backwashed with EA. Subsequently, sublimation purification was carried out to obtain 0.67 g of a pure greenish solid compound 6 in a yield of 58%.

Compound 6 : Mass Spec (FAB) m / z 832 [(M + H) <^+> ]. ^{1 H NMR (400 MHz, CDCl} 3): δ2.16 (s, 6H), 6.43 (d, 2H, J = 8.4Hz), 6.83 (d, 2H, J = 8.4Hz), 7.04 ~ 7.11 (m, (M, 4H), 7.51 (t, 4H, J = 8.0 Hz), 7.59 (t, 2H, J = 8.0 Hz), 7.82-7.84 J = 8.8 Hz), 9.25 (s, 2H)

Compound Synthesis Example 7: Compound 7

[Reaction Scheme 10]

Diphenylamine (0.93 g, 5.50 mmol) was dissolved in 15 ml of dimethylformamide and slowly added to a flask under a stream of nitrogen containing sodium hydride (0.21 g, 8.61 mmol). After stirring for 30 minutes, Intermediate 2 (0.50 g, 1.38 mmol) was dissolved in 15 ml of dimethylformamide and introduced into the above flask. The temperature of the reaction mixture was raised, and the mixture was refluxed for 8 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The resulting solid material was washed with distilled water and then backwashed with EA. Subsequently, sublimation purification was carried out to obtain 0.21 g of a pure yellow solid compound 7 in a yield of 19%.

Compound 7 : Mass Spec (FAB) m / z 808 [(M + H) &lt; ⁺ & gt ^; ]. ^{1 H NMR (400 MHz, CDCl} 3): δ6.63 ~ 6.66 (m, 12H), 6.85 (t, 8H, J = 8.00Hz), 6.95 (t, 2H, J = 7.8Hz), 7.00 ~ 7.54 ( (m, 4H), 7.52 (t, 4H, J = 7.4Hz), 7.57-7.61 (m, 4H), 8.56

Production Example 1: Production of retarded fluorescent organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / DPEPO: Compound 1 / TSPO1 / TPBI / LiF / Al)

The glass substrate on which the anode, ITO, was deposited was ultrasonically cleaned for 30 minutes using pure water and isopropyl alcohol. The cleaned ITO substrate was surface-treated with ultraviolet rays of short wavelength, and then a hole injection layer was formed by spin coating PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)) to a thickness of 60 nm. Thereafter, TAPC (1,1-Bis [4- [N, N'-Di (p-tolyl) Amino] Phenyl] Cyclohexane) was deposited at a pressure of 1 × 10 ^-6 torr at a rate of 0.1 nm / Thereby forming a hole transporting layer. Then, mCP (N, N-dicarbazolyl-3,5-benzene) was deposited at a pressure of 1 × 10 ^-6 torr at a rate of 0.1 nm / s to form a first exciton blocking layer having a thickness of 10 nm. Thereafter, DPEPO (bis [2- (diphenylphosphino) phenyl] ether oxide) was added at a rate of 0.1 nm / s as a host material under a pressure of 1 x 10 ^-6 torr, and the compound synthesized through Synthesis Example 1 1 was co-deposited at a rate of 0.03 nm / s to form a light emitting layer doped with 30% dopant in the host. TSPO1 (diphenylphosphine oxide-4- (triphenylsilyl) phenyl) and TPBi (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene) at a pressure of 1 × 10 ^-6 torr at a rate of 0.1 nm / s To form a second exciton blocking layer and an electron transporting layer of 5 nm and 30 nm, respectively. Thereafter, LiF as an electron injecting material was vapor-deposited at a pressure of ¹ x 10 ^-6 torr at a rate of 0.01 nm / s to form an electron injecting layer of 1 nm. Thereafter, Al was vapor-deposited at a rate of 0.5 nm / sec under a pressure of ¹ x 10 ^-6 torr to form a cathode of 100 nm, thereby forming an organic light-emitting diode. After the device was formed, the device was sealed using a CaO wetting agent and a glass cover glass.

The organic light emitting diode manufactured through Production Example 1 exhibited a maximum quantum efficiency of 24.13% at a voltage of 4.0 V and exhibited excellent efficiency characteristics.

Production Example 2: Production of retarded fluorescent organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / DPEPO: Compound 2 / TSPO1 / TPBI / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that Compound 2 synthesized through Synthesis Example 2 was used as a retardation fluorescent dopant material in the light emitting layer.

The organic light emitting diode manufactured through Production Example 2 exhibited a maximum quantum efficiency of 25.45% at a voltage of 4.5 V and exhibited excellent efficiency characteristics.

Production Example 3: Production of retarded fluorescent organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / mCP: DPEPO: Compound 3 / TSPO1 / TPBI / LiF / Al)

In forming the light emitting layer, Compound 3 synthesized through Synthesis Example 3 as a retardation dopant material at a rate of 0.1 nm / s as mCP and DPEPO as a host material at a pressure of 1 x 10 ^-6 torr was irradiated at a rate of 0.002 nm / s And the organic light emitting diode was fabricated in the same manner as in Preparation Example 1, except that the light emitting layer doped with 1% of dopant was formed on the host.

The organic light emitting diode manufactured through Production Example 3 showed a maximum efficiency of 11.33% at a voltage of 5.0 V and exhibited excellent efficiency characteristics.

Production Example 4: Production of retarded fluorescent organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / DPEPO: Compound 4 / TSPO1 / TPBI / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that Compound 4 synthesized through Synthesis Example 4 was used as a retardation fluorescent dopant material in the light emitting layer.

The organic light emitting diode manufactured through Production Example 4 exhibited a maximum quantum efficiency of 17.8% at a voltage of 4.0 V and exhibited excellent efficiency characteristics.

Production Example 5: Production of retarded fluorescent organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / DPEPO: Compound 5 / TSPO1 / TPBI / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that Compound 5 synthesized through Synthesis Example 5 was used as a retardation fluorescent dopant material in the light emitting layer.

The organic light emitting diode manufactured through Production Example 5 exhibited a maximum quantum efficiency of 18.9% at a voltage of 4.0 V and exhibited excellent efficiency characteristics.

Production Example 6: Production of retarded fluorescent organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / DPEPO: Compound 6 / TSPO1 / TPBI / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that Compound 6 synthesized through Synthesis Example 6 was used as a retardation fluorescent dopant material in the light emitting layer.

The organic light emitting diode manufactured through Production Example 6 exhibited a maximum quantum efficiency of 21.31% at a voltage of 4.5 V and exhibited excellent efficiency characteristics.

Production Example 7: Preparation of retarded fluorescent organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / mCP: DPEPO: Compound 7 / TSPO1 / TPBI / LiF / Al)

In forming the light emitting layer, Compound 7 synthesized through Synthesis Example 7 as a retardation dopant at a rate of 0.1 nm / s as mCP and DPEPO as host materials at a pressure of 1 x 10 ^-6 torr was irradiated at 0.010 nm / s The organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that a light emitting layer doped with a dopant of 5% was formed in the host.

The organic light emitting diode manufactured through Production Example 7 showed a maximum quantum efficiency of 12.66% at a voltage of 4.0 V and exhibited excellent efficiency characteristics.

Comparative Example 1: Manufacture of organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / DPEPO: Compound 6 / TSPO1 / TPBI / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that the following compound 6 was used as a retardation fluorescent dopant material in the light emitting layer.

The organic light emitting diode manufactured through the comparative example showed a maximum quantum efficiency of 4.2% at a voltage of 4.5 V.

<Compound 8>

[Delta] Est of the compounds used as the light emitting material in the above Examples and Comparative Examples and the efficiency and lifetime characteristics of the organic light emitting diodes according to the above Examples and Comparative Examples are summarized in the following table.

△ Est Driving voltage
(100 cd / m2) Quantum efficiency
(%) Lifetime (based on 500 cd / m2) ratio Example 1 0.16 5.17 24.1 15 Example 2 0.12 5.93 25.5 90 Example 3 0.06 5.27 11.3 10 Example 4 0.25 4.8 17.8 6 Example 5 0.27 4.9 18.9 52 Example 6 0.13 5.62 21.31 Example 7 0.24 5.91 12.66 Comparative Example 0.26 10.0 4.2 One

Referring to Table 1, it can be seen that the organic light emitting diode according to the embodiments of the present invention has a significantly lower driving voltage than the organic light emitting diode according to the comparative example, and the quantum efficiency and lifetime are greatly improved. This indicates that the compounds 1 to 7 used in the present Experimental Examples were synthesized by coupling triazine, which is an excepter unit having excellent structural stability, to a benzene ring and connecting two or more donor units such as carbazole to the benzene ring, It is understood that the electron-accepting structure is formed in the molecular structure and the charge-transporting complex form is formed in the molecular structure. As a result, the singlet energy and the triplet energy difference, that is, the narrow? Est, were exhibited, and the organic light emitting diodes of the present experimental examples improved the quantum efficiency and lifetime compared with the comparative example.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, This is possible.

Claims (14)

An organic material for an organic light emitting diode represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently a C5 to C30 aryl group or a C5 to C30 alkylaryl group and R ₁ and R ₂ are not fused to each other or fused together with the nitrogen to which they are attached to form a saturated or unsaturated ring Lt; / RTI &gt;
n is an integer of 2 or 3,
R ₃ to R ₁₂ are each independently hydrogen, deuterium, a C 1 to C 30 alkyl group, or NR ₁₃ R ₁₄ ,
R ₁₃ and R ₁₄ are each independently an aryl group of C5 to C30, or C5 to an alkylaryl group of C30, R ₁₃ and R ₁₄ are either not fused together or fused to a saturated or unsaturated ring together with the to which they are attached to a nitrogen . The method according to claim 1,
Wherein the organic material is a delayed fluorescent light emitting material. The method according to claim 1,
Wherein NR ₁ R ₂ and NR ₁₃ R ₁₄ are the following functional groups regardless of each other.

In the functional group 1, the functional group 2, or the functional group 3, A ₁ and A ₂ are each independently hydrogen, deuterium, or a C1 to C4 alkyl group. The method according to claim 1,
Wherein the organic material represented by Formula 1 is an organic material represented by Formula 2:
(2)

In Formula 2, R _1a , R _2a , R _1b , and R _2b are each independently a C5 to C30 aryl group or a C5 to C30 alkylaryl group; R _1a and R _2a are not fused to each other or fused together with the nitrogen to which they are attached to form a saturated or unsaturated ring; R _1b and R _2b are not fused to each other or fused together with the nitrogen to which they are attached to form a saturated or unsaturated ring,
R ₃ to R ₁₂ are the same as defined in formula (1). The method of claim 4,
The organic material represented by Formula 2 is an organic material having the following Formula 4:

. The method of claim 4,
The organic material represented by Formula 2 is an organic material having the following Formula 5:

. The method according to claim 1,
Wherein the organic material represented by Formula 1 is an organic material represented by Formula 3:
(3)

Wherein R _1a , R _2a , R _1b , R _2b , R _1c and R _2c are each independently a C5 to C30 aryl group or a C5 to C30 alkylaryl group; R _1a and R _2a are not fused to each other or fused together with the nitrogen to which they are attached to form a saturated or unsaturated ring; R _1b and R _2b are not fused to each other or fused together with the nitrogen to which they are attached to form a saturated or unsaturated ring; R _1c and R _2c are not fused to each other or fused together with the nitrogen to which they are attached to form a saturated or unsaturated ring,
R ₃ to R ₁₂ are the same as defined in formula (1). The method of claim 7,
Wherein the organic material represented by Formula 3 is an organic material having the following Formula 1:

. The method of claim 7,
The organic material represented by Formula 3 is an organic material having the following Formula 2:

The method of claim 7,
The organic material represented by Formula 3 is an organic material having the following Formula 3:

. The method of claim 7,
The organic material represented by Formula 3 is an organic material having the following Formula 6:

. The method of claim 7,
The organic material represented by Formula 3 is an organic material having the following Formula 7:

. An organic light emitting diode comprising an anode, a hole conduction layer, a light emitting layer, an electron conduction layer, and a cathode sequentially stacked,
Wherein one of the hole transporting layer, the light emitting layer and the electron transporting layer comprises the organic material of claim 1. 14. The method of claim 13,
Wherein the light emitting layer comprises a host material and a dopant material,
Wherein the dopant material comprises the organic material of claim 1.

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