CN108342191B - Organic electroluminescent compound - Google Patents

Organic electroluminescent compound Download PDF

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CN108342191B
CN108342191B CN201710058770.5A CN201710058770A CN108342191B CN 108342191 B CN108342191 B CN 108342191B CN 201710058770 A CN201710058770 A CN 201710058770A CN 108342191 B CN108342191 B CN 108342191B
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organic electroluminescent
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electroluminescent compound
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王历平
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EverDisplay Optronics Shanghai Co Ltd
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Abstract

The invention provides an organic electroluminescent compound, which has a structure shown in the following formula (I) or (II):
Figure DDA0001217699140000011
wherein R is1～R4Selected from: H. halogen, cyano, C1-C20 chain alkyl, C1-C20 halogenated chain alkyl, C3-C20 naphthenic base, C3-C20 halogenated naphthenic base, C1-C20 alkoxy, C1-C20 silyl, aryloxy with 6-30 ring carbon atoms, aromatic hydrocarbon with 6-30 ring carbon atoms and heterocyclic aromatic hydrocarbon with 6-30 ring carbon atoms; ar (Ar)1And Ar2Each independently selected from: an aromatic hydrocarbon group having 6 to 30 ring-forming carbon atoms and a heterocyclic aromatic hydrocarbon group having 6 to 30 ring-forming carbon atoms. The organic electroluminescent compound has excellent electron blocking performance and higher glass transition temperature; the OLED device prepared by the organic electroluminescent compound has lower working voltage, higher current efficiency and longer service life; therefore, the method has wide application value and excellent market potential.

Description

Organic electroluminescent compound
Technical Field
The invention relates to an organic electroluminescent material, in particular to an organic electroluminescent compound.
Background
Organic Light-Emitting Diodes (hereinafter abbreviated as "OLEDs") have the self-Emitting property, and compared with liquid crystal display technologies, have the great advantages of high contrast, wide viewing angle, fast response, low power consumption, good color reproducibility, and capability of realizing flexible devices, and are widely and commercially applied in the fields of display and illumination.
In the OLED device, the most critical performance indexes are the service life, current efficiency, operating voltage, and color value that can be achieved of the OLED device. To improve the performance of the OLED device in these aspects, the existing OLED device generally adopts a multi-layer structure, which includes: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In order to lower the operating voltage and improve current efficiency and lifetime, the HTL, HBL and EBL are generally required to have higher hole mobility, appropriate energy levels and higher glass transition temperatures. It is worth mentioning that there is still much room for improvement in emission color values of existing blue OLED devices compared to red and green OLED devices.
Therefore, it is critical to develop and select a suitable organic electroluminescent compound. With the development of organic electroluminescent materials, WO2016006711a1 discloses a fluorenamine derivative as a hole blocking layer material in the prior art, however, an OLED device prepared by using the fluorenamine derivative has low hole mobility and low glass transition temperature, so that the OLED device has a short service life, and high operating voltage and power consumption.
In addition, there are many types of blue fluorescent light emitting materials used in the prior art, particularly aromatic amines containing one or more fused ring aromatic groups and/or indenofluorene groups. Such as pyrene-arylamines disclosed in patent US5153073 and pyrene-arylamines disclosed in WO 2012048780; among these, in addition, a series of arylamine luminescent compounds are disclosed in the prior art, such as benzoindenofluorenamines disclosed in WO 2008006449; and dibenzoindenofluoreneamines as disclosed in WO 2007170847. However, similarly, when the above compounds are applied to a blue OLED, the color purity and the service life are still insufficient, and thus there is a certain room for improvement.
Therefore, the development of a hole blocking layer material or an electron blocking layer material which has higher hole mobility and glass transition temperature, lower working voltage and higher current efficiency, and thus has longer service life has great significance for promoting the development of organic electroluminescent display and lighting technology.
Disclosure of Invention
In view of the various drawbacks and disadvantages of the prior art, the present invention is directed to an organic electroluminescent compound that exhibits a lower operating voltage and higher current efficiency when used in an OLED device, thereby having a longer lifetime.
Accordingly, in a first aspect of the present invention, there is provided an organic electroluminescent compound having a structure represented by the following formula (i) or (ii):
Figure BDA0001217699130000021
wherein R is1～R4Each independently selected from: H. halogen, cyano, C1-C20 alkyl, C1-C20 halogenated alkyl, C3-C20 cycloalkyl, C3-C20 halogenated cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, substituted or unsubstituted aryloxy with 6-30 ring carbon atoms, substituted or unsubstituted aryl with 6-30 ring carbon atoms and substituted or unsubstituted heterocyclic aryl with 6-30 ring carbon atoms;
wherein Ar is1And Ar2Each independently selected from: substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms and substituted or unsubstituted heterocyclic aryl group having 6 to 30 ring-forming carbon atoms.
Preferably, in the above organic electroluminescent compounds, R1～R4Each independently selected from: substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms and substituted or unsubstituted heterocyclic aryl group having 6 to 30 ring-forming carbon atoms.
Further preferably, in the above organic electroluminescent compound, R1～R4Each independently selected from any one of the following groups:
Figure BDA0001217699130000031
Figure BDA0001217699130000041
preferably, in the above organic electroluminescent compound, Ar1And Ar2Each independently selected from any one of the following groups:
Figure BDA0001217699130000051
further preferably, in the above organic electroluminescent compound, Ar1And Ar2Each independently is:
Figure BDA0001217699130000052
still further preferably, the organic electroluminescent compound is selected from any one of:
Figure BDA0001217699130000061
Figure BDA0001217699130000071
in a second aspect of the present invention, there is provided an OLED electron blocking layer, characterized in that it contains the organic electroluminescent compound according to the first aspect of the present invention.
In a third aspect of the present invention, there is provided an OLED hole transport layer, characterized in that it contains the organic electroluminescent compound according to the first aspect of the present invention.
In a fourth aspect of the present invention, there is provided an organic electroluminescent blue light emitting material, characterized in that it contains the organic electroluminescent compound according to the first aspect of the present invention.
In a fifth aspect of the present invention, there is provided an OLED device characterized in that it contains the organic electroluminescent compound according to the first aspect of the present invention.
Therefore, the OLED device prepared by the organic electroluminescent compound shows higher hole mobility and glass transition temperature, has lower working voltage and higher current efficiency, and has longer service life compared with the OLED device in the prior art. Therefore, the organic electroluminescent compound provided by the invention has wide application value and excellent market potential.
Detailed Description
In a first aspect of the present invention, there is provided an organic electroluminescent compound having a structure represented by the following formula (i) or (ii):
Figure BDA0001217699130000081
wherein R is1～R4Each independently selected from: H. halogen, cyano, C1-C20 alkyl, C1-C20 halogenated alkyl, C3-C20 cycloalkyl, C3-C20 halogenated cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, substituted or unsubstituted aryloxy with 6-30 ring carbon atoms, substituted or unsubstituted aryl with 6-30 ring carbon atoms and substituted or unsubstituted heterocyclic aryl with 6-30 ring carbon atoms;
wherein Ar is1And Ar2Each independently selected from: substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms and substituted or unsubstituted heterocyclic aryl group having 6 to 30 ring-forming carbon atoms.
In a preferred embodiment, R in the above organic electroluminescent compounds1～R4Each independently selected from: substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms and substituted or unsubstituted heterocyclic aryl group having 6 to 30 ring-forming carbon atoms.
In a further preferred embodiment, R in the above organic electroluminescent compounds1～R4Each independently selected from any one of the following groups:
Figure BDA0001217699130000082
Figure BDA0001217699130000091
Figure BDA0001217699130000101
in a preferred embodiment, Ar in the above organic electroluminescent compound1And Ar2Each independently selected from any one of the following groups:
Figure BDA0001217699130000102
in a further preferred embodiment, Ar in the above organic electroluminescent compound1And Ar2Each independently is:
Figure BDA0001217699130000103
in a still further preferred embodiment, the organic electroluminescent compound is selected from any one of the following:
Figure BDA0001217699130000111
Figure BDA0001217699130000121
in a second aspect of the invention, there is provided an OLED electron blocking layer comprising an organic electroluminescent compound according to the first aspect of the invention.
In a third aspect of the invention, there is provided an OLED hole blocking layer comprising an organic electroluminescent compound according to the first aspect of the invention.
In a fourth aspect of the present invention, there is provided an organic electroluminescent blue light material comprising the organic electroluminescent compound according to the first aspect of the present invention.
In a fifth aspect of the invention, there is provided an OLED device comprising an organic electroluminescent compound according to the first aspect of the invention.
The present invention will be further illustrated with reference to the following specific embodiments, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified; the starting materials are commercially available from the open literature unless otherwise specified.
EXAMPLE 1 preparation of Compound 8
The method comprises the following steps: synthesis of intermediate 1
Figure BDA0001217699130000122
O-dibromobenzene (23.6g, 100.0mmol) and 2-naphthalene boronic acid (17.2g, 100.0mmol) were dissolved in 200ml of toluene, and 2M aqueous sodium carbonate (50.0ml) and tetrahydrofuran (50.0ml) were added; after air removal by nitrogen sparging, the catalyst tetrakis (triphenylphosphine) palladium (347mg, 3.0mmol) was added quickly; heating to 90 ℃ under the protection of nitrogen, and stirring for reaction overnight; then, ethyl acetate and water were added, and after stirring, standing, and separation, the organic phase was extracted, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure, and subjected to silica gel column chromatography with petroleum ether as eluent to give pure intermediate 1(21.1g, 75.0mmol), which gave a reaction yield of 75%.
Mass spectrometric characterization of intermediate 1: MS [ ESI ]+]m/z＝283.12(C16H11Br, theoretical 282.00). Step two: synthesis of intermediate 2
Figure BDA0001217699130000131
Dissolving magnesium powder (2.0g, 85.0mmol) in diethyl ether, removing air, adding a few drops of 1, 2-dichloroethane, heating for 10 min, and cooling to room temperature; then, intermediate 1(21.1g, 75.0mmol) dissolved in ether was added to the reaction system and heated to reflux for reaction for 3 hours to prepare a grignard reagent.
Then, 4-bromobenzophenone (17.0g, 65.0mmol) was dissolved in ether, the Grignard reagent prepared above was slowly dropped into the reaction system under nitrogen protection, after heating reaction for 12 hours, a small amount of diluted hydrochloric acid was added, extraction was performed, drying was performed, the solvent was removed under reduced pressure, silica gel column chromatography was performed, eluent was petroleum ether, and pure intermediate 2(18.7g, 40.3mmol) was obtained at this step with a reaction yield of 62%.
Mass spectrometric characterization of intermediate 2: MS [ ESI ]+]m/z＝464.95(C29H21BrO，Theoretical 464.08).
Step three: synthesis of intermediate 3
Figure BDA0001217699130000132
Intermediate 2(18.7g, 40.3mmol) was dissolved in 100.0ml of glacial acetic acid, 2.0ml of hydrochloric acid was added, the reaction was stopped after 3 hours of reaction by heating to 130 ℃ under nitrogen, the solid in the reaction solution was filtered off, and the resulting solid was washed with water, aqueous sodium hydroxide solution, water and methanol and dried under vacuum to give intermediate 3(16.9g, 37.9mmol), which was obtained in 94% yield.
Mass spectrometric characterization of intermediate 3: MS [ ESI ]+]m/z＝447.15(C29H19Br, theoretical 446.07). Step four: synthesis of intermediate 7
Figure BDA0001217699130000141
A mixture of 9, 9-diphenyl-9H-fluoren-2-amine (16.7g, 50.0mmol), 4-bromobenzofuran (12.4g, 50.0mmol), bis (dibenzylideneacetone) palladium (860mg, 1.5mmol), tri-tert-butylphosphine (600mg, 3mmol) and toluene (100ml) was heated to 90 ℃ under a stream of argon gas, sodium tert-butoxide (288mg, 3mmol) was added, heated to 110 ℃ under an argon atmosphere and stirred for reaction for 12 hours. Cooling the reaction mixture to room temperature, and adding water for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain intermediate 7(18.2g, 36.5mmol) in 73% yield.
Mass spectrometric characterization of intermediate 7: MS [ ESI ]+]499.98 (theoretical value 499.19, C)37H25NO)。
Step five: synthesis of Compound 8
Figure BDA0001217699130000142
A mixture of intermediate 3(3.7g, 15.0mmol), intermediate 7(9.0g, 18.0mmol), bis (dibenzylideneacetone) palladium (518mg, 0.9mmol), tri-tert-butylphosphine (400mg, 2mmol) and toluene (150ml) was heated to 90 ℃ under a stream of argon gas, sodium tert-butoxide (198mg, 2mmol) was added, and the mixture was heated to 110 ℃ under an argon atmosphere and stirred for 24 hours. Cooling the reaction mixture to room temperature, and adding water for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain the target product compound 8(8.2g, 9.5mmol) in a yield of 63%; it can be further purified by sublimation in vacuo to give 6.5g of Compound 8.
Mass spectrometric characterization of compound 8: MS [ ESI ]+]865.83 (theoretical value 865.33, C)66H43NO)。
EXAMPLE 2 preparation of Compound 2
The method comprises the following steps: intermediate 1 was synthesized, the same as step one in example 1;
step two: intermediate 2 was synthesized, the same as step two in example 1;
step three: intermediate 3 was synthesized, the same as step three in example 1;
step four: synthesis of intermediate 8
Figure BDA0001217699130000151
A mixture of aniline (4.7g, 50.0mmol), 4-bromodibenzofuran (12.4g, 50.0mmol), bis (dibenzylideneacetone) palladium (860mg, 1.5mmol), tri-tert-butylphosphine (600mg, 3mmol) and toluene (100ml) was heated to 90 ℃ under a stream of argon gas, and after addition of sodium tert-butoxide (288mg, 3mmol), the mixture was heated to 110 ℃ under an argon atmosphere and stirred for 12 hours. Then, cooling the reaction mixture to room temperature, and adding water for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain intermediate 8(10.0g, 40.5mmol) in a yield of 81%.
Mass spectrometric characterization of intermediate 8: MS [ ESI ]+]247.85 (theoretical value 246.09, C)17H12NO)。
Step five: synthesis of Compound 2
Figure BDA0001217699130000161
A mixture of intermediate 3(3.7g, 15.0mmol), intermediate 8(4.6g, 18.0mmol), bis (dibenzylideneacetone) palladium (518mg, 0.9mmol), tri-tert-butylphosphine (400mg, 2mmol) and toluene (150ml) was heated to 90 ℃ under a stream of argon gas, sodium tert-butoxide (198mg, 2mmol) was added, and the mixture was heated to 110 ℃ under an argon atmosphere and stirred for 24 hours. Then, cooling the reaction mixture to room temperature, and adding water for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain the objective compound 2(6.3g, 10.0mmol) in a yield of 66%. It can be further purified by sublimation in vacuo to give 4.6g of Compound 2.
Mass spectrometric characterization of compound 2: MS [ ESI ]+]625.65 (theoretical value 625.24, C)47H31NO)。
EXAMPLE 3 preparation of Compound 16
The method comprises the following steps: synthesis of intermediate 4
Figure BDA0001217699130000162
O-dibromobenzene (23.6g, 100.0mmol) and 9-phenanthreneboronic acid (22.2g, 100.0mmol) were dissolved in 200ml of toluene, and a 2M aqueous solution of sodium carbonate (50.0ml), and tetrahydrofuran (50.0ml) were added; after air removal by nitrogen sparging, the catalyst tetrakis (triphenylphosphine) palladium (347mg, 3.0mmol) was added quickly; heating to 90 ℃ under the protection of nitrogen, reacting overnight, adding ethyl acetate and water, stirring, standing, layering, extracting an organic phase, drying with anhydrous magnesium sulfate, removing the solvent under reduced pressure, performing silica gel column chromatography, eluting with petroleum ether to obtain pure intermediate 4(24.0g, 72.3mmol), wherein the reaction yield of the step is 72%.
Mass spectrometric characterization of intermediate 4: MS [ ESI ]+]m/z＝333.52(C20H13Br, theoretical 332.02). Step two: synthesis of intermediate 5
Figure BDA0001217699130000171
Dissolving magnesium powder (1.9g, 82.0mmol) in diethyl ether, removing air, adding a few drops of 1, 2-dichloroethane, heating for 10 min, and cooling to room temperature; intermediate 4(24.0g, 72.3mmol) dissolved in ether was added thereto and heated to reflux for 2.5 hours to prepare a grignard reagent.
Dissolving 4-bromobenzophenone (16.2g, 62.0mmol) in ether, slowly dropping the Grignard reagent prepared above into the reaction system under nitrogen protection, heating for reaction for 14 hours, then adding a small amount of diluted hydrochloric acid, extracting, drying, removing the solvent under reduced pressure, performing silica gel column chromatography, and finally obtaining pure intermediate 5(18.5g, 36.0mmol) with petroleum ether as eluent, wherein the reaction yield of the step is 58%.
Mass spectrometric characterization of intermediate 5: MS [ ESI ]+]m/z＝515.19(C33H23BrO, theoretical 514.09).
Step three: synthesis of intermediate 6
Figure BDA0001217699130000172
Intermediate 5(18.5g, 36.0mmol) was dissolved in 80.0ml of glacial acetic acid and 1.8ml of hydrochloric acid was added, heated to 130 ℃ under nitrogen, the reaction was stopped after 2.5 hours, the solid in the reaction was filtered off and washed with water, aqueous sodium hydroxide solution, water and methanol and dried under vacuum to give intermediate 6(15.3g, 30.9mmol) which gave 86% yield.
Mass spectrometric characterization of intermediate 6: MS [ ESI ]+]m/z＝497.08(C33H21Br, theoretical 496.08). Step four: intermediate 7 was synthesized, the same as step four in example 1;
step five: synthesis of Compound 16
Figure BDA0001217699130000181
A mixture of intermediate 6(7.4g, 15.0mmol), intermediate 7(9.0g, 18.0mmol), bis (dibenzylideneacetone) palladium (518mg, 0.9mmol), tri-tert-butylphosphine (400mg, 2mmol) and toluene (150ml) was heated to 90 ℃ under a stream of argon gas, followed by addition of sodium tert-butoxide (198mg, 2mmol) and heating to 110 ℃ under an argon atmosphere and stirring for 24 hours. Cooling the reaction mixture to room temperature, and adding water for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain the objective compound 16(8.0g, 8.7mmol) in a yield of 58%. Further, it can be further purified by sublimation in vacuo to give 6.2g of compound 16.
Mass spectrometry characterization of compound 16: MS [ ESI ]+]915.45 (theoretical value 915.35, C)70H45NO)。
EXAMPLE 4 preparation of Compound 10
The method comprises the following steps: intermediate 4 was synthesized, the same as step one in example 3;
step two: intermediate 5 was synthesized, the same as step two in example 3;
step three: intermediate 6 was synthesized, the same as step three in example 3;
step four: intermediate 8 was synthesized, the same as step four in example 2;
step five: synthesis of Compound 10
Figure BDA0001217699130000182
A mixture of intermediate 6(7.4g, 15.0mmol), intermediate 8(4.6g, 18.0mmol), bis (dibenzylideneacetone) palladium (518mg, 0.9mmol), tri-tert-butylphosphine (400mg, 2mmol) and toluene (150ml) was heated to 90 ℃ under a stream of argon gas, followed by addition of sodium tert-butoxide (198mg, 2mmol) and heating to 110 ℃ under an argon atmosphere and stirring for 24 hours. Cooling the reaction mixture to room temperature, and adding water for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain the objective compound 10(5.6g, 8.3mmol) in 55% yield. Further, it can be further purified by sublimation in vacuo to obtain 3.8g of compound 10.
Mass spectrometric characterization of compound 10: MS [ ESI ]+]675.34 (theoretical value 675.26, C)51H33NO)。
Example 5 preparation of an OLED device containing Compound 8
The glass substrate with ITO transparent electrodes at 25 × 75x1.1mm was ultrasonically cleaned in isopropanol for 10 minutes, followed by UV ozone cleaning for 30 minutes.
The cleaned glass substrate with the ITO transparent electrode is arranged on a substrate bracket of a vacuum evaporation device,
first, an electron accepting compound HI was deposited on a glass substrate so as to cover the ITO transparent electrode, and a hole injection layer of 5nm was formed
Then, depositing 150nm of aromatic compound HT as a hole transport layer on the hole injection layer;
then, compound 8 with the thickness of 10nm is evaporated on the hole transport layer to be used as an electron blocking layer;
then, co-evaporating a host compound BH and a dopant compound BD as a light emitting layer on the hole transport layer at a thickness of 25 nm; wherein the mass concentration of BD is 5%;
then, ET-1: ET-2 (mass ratio: 1) with a thickness of 35nm was deposited on the light-emitting layer as an electron transport layer, ET-2 with a thickness of 2nm was deposited as an electron injection layer, and aluminum with a thickness of 120nm was deposited as a cathode.
Therefore, the device structure of the OLED is simply as follows:
ITO/HI(5nm)/HT(150nm)/EBL(10nm)/BH:BD(25nm,5％wt)/ET-1:ET-2(35nm,1:1)/ET-2(2nm)/Al(120nm)
the compounds HI, HT, BH, BD, ET-1 and ET-2 involved in the preparation process of the OLED device are respectively compounds with the structures shown as follows:
Figure BDA0001217699130000201
example 6 preparation of OLED devices containing Compound 2
The fabrication procedure for this OLED device was the same as in example 5, with the only difference that compound 2 was used for the electron blocking layer.
Example 7 preparation of an OLED device containing Compound 16
The fabrication procedure for this OLED device was the same as in example 5, with the only difference that compound 16 was used for the electron blocking layer.
Example 8 preparation of an OLED device containing Compound 10
The fabrication procedure for this OLED device was the same as in example 5, with the only difference that compound 10 was used for the electron blocking layer.
Comparative example for OLED device preparation
In this comparative example, the fabrication procedure for an OLED device was the same as that of example 5, the only difference being that the electron blocking layer was a comparative compound having the formula shown below:
Figure BDA0001217699130000211
to characterize the performance of each of the above OLED devices, the inventors conducted related performance tests: the electroluminescence spectra were recorded at various currents and voltages, and the current efficiency (cd/A) of the luminous density function was calculated from the current/voltage/luminous density characteristic lines (IUL characteristic lines) which exhibited Lambert emission characteristics, at a luminance of 500cd/m2The electroluminescence spectra were recorded and the color coordinates of CIE1931x and y were calculated by itself. Specific performance test results are shown in table 1:
Figure BDA0001217699130000212
TABLE 1
As can be seen from table 1 above, the use of the organic electroluminescent compound according to the present invention as an electron blocking layer in a blue OLED device exhibits a lower operating voltage, higher current efficiency, and thus a longer lifespan, as compared to the comparative example.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (4)

1. An organic electroluminescent compound, characterized in that the organic electroluminescent compound is selected from any one of the following:
Figure FDA0002636694250000011
2. an OLED electron blocking layer comprising the organic electroluminescent compound according to claim 1.
3. An organic electroluminescent blue light emitting material comprising the organic electroluminescent compound according to claim 1.
4. An OLED device comprising the OLED electron blocking layer of claim 2.
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CN103086949A (en) * 2011-11-01 2013-05-08 财团法人工业技术研究院 Carbazole derivative and organic light emitting diode comprising the same
KR20160052136A (en) * 2014-11-04 2016-05-12 덕산네오룩스 주식회사 Display device using a composition for organic electronic element, and an organic electronic element thereof

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KR20100112903A (en) * 2009-04-10 2010-10-20 주식회사 엘지화학 New compounds and organic electronic device using the same
CN103086949A (en) * 2011-11-01 2013-05-08 财团法人工业技术研究院 Carbazole derivative and organic light emitting diode comprising the same
KR20160052136A (en) * 2014-11-04 2016-05-12 덕산네오룩스 주식회사 Display device using a composition for organic electronic element, and an organic electronic element thereof

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