CN113979920A - Indolo spirofluorene organic compound, organic electroluminescent device and display device - Google Patents

Indolo spirofluorene organic compound, organic electroluminescent device and display device Download PDF

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CN113979920A
CN113979920A CN202111406006.5A CN202111406006A CN113979920A CN 113979920 A CN113979920 A CN 113979920A CN 202111406006 A CN202111406006 A CN 202111406006A CN 113979920 A CN113979920 A CN 113979920A
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spirofluorene
indolo
organic compound
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任俊
李志强
王占奇
丁言苏
陆金波
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Fuyang Sineva Material Technology Co Ltd
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Abstract

The organic compound can be used as a phosphorescent main body material or a hole transport material of a light emitting layer of an OLED light emitting device, the organic electroluminescent device has lower driving voltage and high current efficiency and has longer service life as the hole transport material, and the device has lower driving voltage and high current efficiency as the main body material of the light emitting layer.

Description

Indolo spirofluorene organic compound, organic electroluminescent device and display device
Technical Field
The invention belongs to the field of electroluminescence, and particularly relates to an indolo spirofluorene compound, an organic electroluminescent device and a display device.
Background
Currently, organic electroluminescent (OLED) display technology has been applied in the fields of smart phones, tablet computers, and the like, and further will be expanded to large-size application fields such as televisions. In the development process of the last 30 years, various OLED materials with excellent performance are developed, and the commercialization process of the OLED is accelerated by different designs of the device structure and optimization of the device life, efficiency and other properties, so that the OLED is widely applied in the fields of display and illumination.
The selection of the hole layer, the light-emitting layer and other organic functional layer materials also has a great influence on the current efficiency, the driving voltage and the lifetime of the device, and functional layer materials with higher performance are still being explored.
Therefore, in order to meet the higher requirements of people for OLED devices, the development of more various and higher-performance OLED materials is urgently needed in the art.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an indolocairofluorene organic compound, an organic electroluminescent device and a display device. The organic compound can be used as a phosphorescent host material or a hole transport material of an OLED (organic light emitting diode) light emitting device.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an indolo spirofluorene organic compound having a structure represented by the following formula (I):
Figure BDA0003372840840000021
Ar1selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C5-C40 heteroaryl or substituted or unsubstituted C1-C12 alkyl;
Ar2selected from substituted or unsubstituted aryl of C6-C40, substituted or unsubstituted C5-C40 is heteroaryl;
Ar3is selected from substituted or unsubstituted aryl of C6-C40;
Ar2and Ar3Alone or Ar2And Ar3The carbon atom hybridized by the middle SP2 is connected with a ring through a single bond;
and when Ar is1Selected from phenyl, Ar2And Ar3When one is selected from biphenyl, Ar2And Ar3The other is not biphenyl,
Figure BDA0003372840840000022
When Ar is1When selected from phenyl, Ar2And Ar3Is not simultaneously
Figure BDA0003372840840000023
And when Ar is1When selected from phenyl, Ar2And Ar3One of them is selected from
Figure BDA0003372840840000024
While the other is not selected from
Figure BDA0003372840840000025
When Ar is1When selected from phenyl, Ar2And Ar3One of them is selected from
Figure BDA0003372840840000026
While the other is not selected from
Figure BDA0003372840840000027
When the substituted or unsubstituted group contains a substituent, the substituent is selected from F, CN, deuterium, alkyl of C1-C6, alkoxy of C1-C6 and aryl of C6-C40.
In the present invention, the definition of a group defines the range of the number of carbon atoms, the number of carbon atoms of which is any integer within the defined range, for example, C6-C40 aryl, the number of carbon atoms representing the aryl group can be any integer within the range of 6-40, for example, 6, 8, 10, 15, 20, 30, 35, 38 or 40, etc., and the definition of the number of carbon atoms of other groups, in turn, has the same meaning.
Preferably, Ar1And Ar2At least one heteroaryl group selected from substituted or unsubstituted C5-C40.
Preferably, the aryl group of C6 to C40 is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzindenfluorenyl, dibenzoindenofluorenyl, naphthofluorenyl or benzonaphthofluorenyl, or a combination of one or more groups thereof.
Preferably, the heteroaryl group of C5-C40 is selected from dibenzofuranyl, dibenzothienyl, naphthodibenzofuranyl, naphthodibenzothienyl, benzonaphthodibenzofuranyl, or benzonaphthodibenzothienyl.
Preferably, Ar1Selected from phenyl, biphenyl, methyl, ethyl, propyl, butyl, pentyl or hexyl.
Preferably, Ar2Selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzindenenyl, dibenzoindenofluorenyl, naphthofluorenyl, benzonaphthyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuranyl, or benzodibenzothiophenyl.
Preferably, the indolo spirofluorene organic compound is any one of the following compounds:
Figure BDA0003372840840000031
Figure BDA0003372840840000041
Figure BDA0003372840840000051
in the present invention, the synthetic route of the organic compound is as follows:
Figure BDA0003372840840000061
in another aspect, the present invention provides a light-emitting layer comprising the indolo spirofluorene organic compound as described above.
In another aspect, the present invention provides a hole transport layer comprising the indolo spirofluorene organic compound as described above.
In another aspect, the present invention provides an organic electroluminescent device comprising the indolo spirofluorene organic compound as described above.
Preferably, the organic electroluminescent device comprises an anode, a cathode and an organic thin film layer arranged between the anode and the cathode, wherein the organic thin film layer comprises the indolo spirofluorene organic compound.
Preferably, the organic thin film layer includes a hole transport layer including the indolo spirofluorene-based organic compound as described above.
Preferably, the organic thin film layer includes a light emitting layer including the organic compound as described above.
In the invention, the indolo spirofluorene organic compound is used as a phosphorescent host material of a light-emitting layer.
In another aspect, the present invention provides a display apparatus comprising the organic electroluminescent device as described above.
Compared with the prior art, the invention has the following beneficial effects:
the organic compound can be used as a phosphorescent main body material or a hole transport material of a light-emitting layer of an OLED light-emitting device, the organic electroluminescent device has lower driving voltage (below 5.11V), high current efficiency (above 33.2 cd/A) and longer service life (above 62h, even above 109 h) as the hole transport material, and the device has lower driving voltage (below 5.56V) and high current efficiency (above 8.76 cd/A) as the main body material of the light-emitting layer.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Synthesis example 1 Synthesis of Compound 1
Figure BDA0003372840840000071
Into a 250mL three-necked flask, M-1-1(5.6g, 0.01mol) and M-1-2(2.5g, 0.01mol) were added, 100mL of toluene was added, and sodium tert-butoxide (1.2g, 0.013mol), Pd and the mixture were added under stirring2(dba)3(0.046g, 0.00005mol), replacing nitrogen, adding 0.2g of tri-tert-butylphosphine 10% toluene solution, starting heating, slowly heating to 80 ℃ (keeping nitrogen protection in the reaction process), reacting for 2 hours, and detecting by HPLC (M-1)<1 percent), stopping the reaction and cooling to room temperature. Washing with salt water for 2 times, adding anhydrous sodium sulfate into organic phase, and drying; performing column chromatography with toluene as eluent; concentration to give crude product, recrystallization from toluene to give 5.7g of Compound 1, HPLC purity>99％。
Mass spectrum detection is carried out on the compound 1, and the molecule m/z is determined to be: 724.29.
compound 1 was subjected to nuclear magnetic detection and the data was resolved as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)3)：δ8.57(m，1H)，δ8.34(s，1H)δ8.22(s，1H)，δ8.19(d，1H)，δ7.86(m，2H)，δ7.80～7.72(m，4H)，δ7.67～7.34(m，15H)，δ7.28～7.18(m，6H)，δ7.17～7.05(m，4H)，δ6.99(m，1H)。
Synthesis example 2 Synthesis of Compound 7
Figure BDA0003372840840000081
Synthesis method reference was made to the synthesis of Compound 1 in example 1 except that the compound represented by M-1-2 was changed to the compound represented by M-7-2.
Mass spectrum detection was performed on compound 7 to determine the molecule m/z as: 864.31.
synthesis example 3 Synthesis of Compound 21
Figure BDA0003372840840000082
Synthesis method refer to the synthesis of Compound 1 in example 1, except that the compound represented by M-1-2 is replaced by a compound represented by M-21-2.
Mass spectrometry was performed on compound 21 to determine the molecule m/z as: 722.27.
synthesis example 4 Synthesis of Compound 26
Figure BDA0003372840840000083
Synthesis method reference was made to the synthesis of Compound 1 in example 1 except that the compound represented by M-1-2 was changed to the compound represented by M-26-2.
Mass spectrometric detection of compound 26 determined to have a molecule m/z: 762.30.
synthesis example 5 Synthesis of Compound 31
Figure BDA0003372840840000091
Synthesis method refer to the synthesis of Compound 1 in example 1, except that the compound represented by M-1-2 is replaced by a compound represented by M-31-2.
Mass spectrometric detection of compound 31 determined to have a molecule m/z: 736.25.
synthesis example 6 Synthesis of Compound 41
Figure BDA0003372840840000092
(1) Synthesis of Compound M-41-1:
a500-ml three-necked flask was charged with nitrogen, 200 ml of acetone, 4.84g (0.01mol) of the compound represented by formula M-41-0, 2.18 g (0.02mol) of bromoethane and 1g (0.025mol) of sodium hydroxide were added, the mixture was stirred at room temperature for 48 hours, water and dichloromethane were added for liquid separation, the organic layer was washed with water to neutrality, dried over magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and recrystallized from a mixed solvent of methanol and chloroform to give 4.6 g of the compound represented by formula M-41-1.
The intermediate shown as the formula M-41-1 is subjected to mass spectrum detection, and two peaks with the largest M/z are as follows: 511.09, 513.09, determining the molecular formula of the product as C33H22BrN。
Figure BDA0003372840840000101
(2) Synthesis of compound 41:
synthesis method referring to the synthesis of Compound 1 in example 1, except that the compound represented by M-1-2 was changed to the compound represented by M-41-2 and the compound represented by M-1-1 was changed to the compound represented by M-41-1.
Mass spectrometry was performed on compound 41 to determine the molecule m/z as: 676.29.
synthesis example 7 Synthesis of Compound 57
Figure BDA0003372840840000102
Synthesis method reference was made to the synthesis of Compound 1 in example 1 except that the compound represented by M-1-2 was changed to the compound represented by M-57-2.
Mass spectrometric detection of compound 57 was carried out to determine the molecule m/z as: 789.31.
synthesis example 8 Synthesis of Compound 60
Figure BDA0003372840840000103
(1) Synthesis of intermediate M-60-1
Under the protection of nitrogen, M-41-0(4.84g, 0.01mol) and 2-iodobiphenyl (2.80g, 0.01mol) were added to a 250mL three-necked flask, 50mL of DMF was added, potassium hydroxide (0.84g, 0.015mol) and cuprous iodide (2g) were added with stirring, the mixture was heated to 150 ℃ and reacted for 6 hours to stop the reaction, the reaction solution was cooled, 50mL of water was added to precipitate a solid, the crude product was obtained by filtration and recrystallized with toluene to obtain 3.1g of intermediate M-60-1, the HPLC purity was 98%.
The intermediate shown as the formula M-60-1 is subjected to mass spectrum detection, and two peaks with the largest M/z are as follows: 635.12, 637.12, the molecular formula of the product is determined to be C43H26 BrN.
Figure BDA0003372840840000111
(2) Synthesis of compound 60:
synthesis method referring to the synthesis of Compound 1 in example 1, except that the compound represented by M-1-2 was changed to the compound represented by M-60-2 and the compound represented by M-1-1 was changed to the compound represented by M-60-1.
Mass spectrometric detection of compound 60 determined the molecule m/z to be: 814.30.
likewise, other compounds of the present invention can be prepared by the same preparation method as the above compounds, for example, compounds 2, 3, 25, 29 and 50 can be prepared similarly, and the molecular correctness can be determined by mass spectrometry.
The compound used in the device examples had the following structure, and all organic OLED materials were sublimed to HPLC purity above 99.99%.
Figure BDA0003372840840000121
Device example 1
The application example provides an OLED device, and the preparation method of the OLED device comprises the following steps:
(1) a transparent electrode Indium Tin Oxide (ITO) film (15 Ω/sq, Samsung Corning, Samsung) on a glass substrate for an Organic Light Emitting Diode (OLED) device was sequentially ultrasonically cleaned with trichloroethylene, acetone, ethanol, and distilled water, and then stored in isopropyl alcohol; and mounting the ITO substrate on a substrate clamp of vacuum vapor deposition equipment.
(2) In a chamber of a vacuum vapor deposition apparatus, a chamber pressure is up to 10-6After that, the HIL material was vacuum-evaporated to form a hole injection layer having a thickness of 60nm on the ITO substrate.
(3) On the hole injection layer formed above, compound 1 was vacuum-evaporated to form a hole transport layer having a thickness of 20 nm.
(4) On the hole transport layer formed above, compounds I-40 and D-1 were vacuum-evaporated to form a light-emitting layer having a thickness of 30 nm. Wherein the volume ratio of CBP to D-1 is 90: 10.
(5) on the light-emitting layer formed above, ETL was vacuum-evaporated, thereby forming an electron transport layer having a thickness of 30nm on the light-emitting layer.
(6) 8-hydroxyquinolinolato lithium (EIL) with a thickness of 2nm is vacuum-evaporated on the electron transport layer to form an electron injection layer EIL.
(7) Vacuum evaporating an Al cathode with the thickness of 150nm on the electron injection layer; and obtaining the OLED device.
Device examples 2 to 8
The device was prepared in the same manner as in device example 1 except that the hole transport material was different, as detailed in table 1.
Comparative device examples 1 to 3
The device was prepared in the same manner as in device example 1 except that the hole transport material was different, as detailed in table 1.
Performance testing of OLED devices
Testing the driving voltage, the current efficiency and the service life LT90 of the OLED device provided above by using an OLED-1000 multichannel accelerated aging life and light color performance analysis system produced in Hangzhou distance; here, LT90 indicates the time required for the luminance to decrease to 90% of the original luminance with the current density kept unchanged at 1000nit of the original luminance.
The specific test results are shown in table 1:
TABLE 1
Figure BDA0003372840840000141
As can be seen from Table 1, when the compound of the present invention is used as a hole transport material, the OLED device can have a lower driving voltage (below 5.11V), and simultaneously has a high current efficiency (above 33.2 cd/A) and a long lifetime (above 62h, even as high as above 109 h).
Device examples 12-15 and comparative example 4
In the examples, the compound of the present invention was used as a blue light host material in an organic electroluminescent device, and in the comparative examples, CBP was used as a blue light host material in an organic electroluminescent device.
The structure of the organic electroluminescent device is as follows: ITO/HIL (50nm)/HTL (20 nm)/blue host material (35 nm): firpic [ 8% ]/ETL (10nm)/Alq3(15nm)/LiF (0.5nm)/Al (150 nm). Wherein "Firpic [ 8% ]" means the doping ratio of the blue dye, i.e. the volume ratio of the blue host material to Firpic is 100: 8.
The preparation process of the organic electroluminescent device is as follows: the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, vacuumizing to 1 x 10 < -5 > to 9 x 10 < -4 > Pa, and performing vacuum evaporation on the anode layer film to form a hole injection layer HIL, wherein the evaporation rate is 0.01nm/s, and the evaporation film thickness is 50 nm;
vacuum evaporating a hole transport layer HTL on the hole injection layer, wherein the evaporation rate is 0.01nm/s, and the evaporation film thickness is 20 nm;
vacuum evaporating blue light main body materials and dyes Firpic on the hole transport layer to be used as a light emitting layer of the organic electroluminescent device, wherein the evaporation rate is 0.01nm/s, and the total film thickness of the evaporation is 35 nm; (ii) a
Sequentially vacuum evaporating an electron transport layer ETL and Alq3 on the luminescent layer, wherein the evaporation rates are both 0.01nm/s, and the evaporation film thicknesses are respectively 10nm and 15 nm;
and (3) evaporating LiF with the thickness of 0.5nm and Al with the thickness of 150nm on the electron transport layer in vacuum to be used as an electron injection layer and a cathode.
All the organic electroluminescent devices are prepared by the method, and the differences only lie in the selection of blue light main body materials, and the details are shown in the following table 2.
And (3) performance testing:
the brightness, driving voltage and current efficiency of the prepared organic electroluminescent device were measured using the Hangzhou remote-produced OLED-1000 multichannel accelerated aging life and photochromic performance analysis system, and the test results are shown in Table 2 below.
TABLE 2
Figure BDA0003372840840000151
Figure BDA0003372840840000161
As can be seen from Table 2, when the compound of the present invention is used as a blue host material, the OLED device can have a lower driving voltage (below 5.56V) and a high current efficiency (above 8.76 cd/A).
The applicant states that the present invention is illustrated by the above examples of the organic compound, the organic electroluminescent device and the display device of the present invention, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. An indolo spirofluorene organic compound having a structure represented by the following formula (I):
Figure FDA0003372840830000011
Ar1selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C5-C40 heteroaryl or substituted or unsubstituted C1-C12 alkyl;
Ar2selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C5-C40 heteroaryl;
Ar3is selected from substituted or unsubstituted aryl of C6-C40;
Ar2and Ar3Alone or Ar2And Ar3The carbon atom hybridized by the middle SP2 is connected with a ring through a single bond;
and when Ar is1Selected from phenyl, Ar2And Ar3When one is selected from biphenyl, Ar2And Ar3The other is not biphenyl,
Figure FDA0003372840830000012
When Ar is1When selected from phenyl, Ar2And Ar3Is not simultaneously
Figure FDA0003372840830000013
And when Ar is1When selected from phenyl, Ar2And Ar3One of them is selected from
Figure FDA0003372840830000014
While the other is not selected from
Figure FDA0003372840830000015
When Ar is1When selected from phenyl, Ar2And Ar3One of them is selected from
Figure FDA0003372840830000016
While the other is not selected from
Figure FDA0003372840830000017
When the substituted or unsubstituted group contains a substituent, the substituent is selected from F, CN, deuterium, alkyl of C1-C6, alkoxy of C1-C6 and aryl of C6-C40.
2. The indolo spirofluorene organic compound according to claim 1, wherein Ar is Ar1And Ar2At least one heteroaryl group selected from substituted or unsubstituted C5-C40.
3. The indoorospirofluorene organic compound according to claim 1 or 2, wherein the aryl group having 6-C40 is selected from one or a combination of two or more of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzindenofluorenyl, naphthofluorenyl, or benzonaphthofluorenyl;
preferably, the heteroaryl group of C5-C40 is selected from dibenzofuranyl, dibenzothienyl, naphthodibenzofuranyl, naphthodibenzothienyl, benzonaphthodibenzofuranyl, or benzonaphthodibenzothienyl.
4. The indolo spirofluorene organic compound according to any one of claims 1 to 3, wherein Ar is Ar1Selected from phenyl, biphenyl, and methylAlkyl, ethyl, propyl, butyl, pentyl or hexyl.
5. The indolo spirofluorene organic compound according to any one of claims 1 to 4, wherein Ar is Ar2Selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzindenenyl, dibenzoindenofluorenyl, naphthofluorenyl, benzonaphthyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuranyl, or benzodibenzothiophenyl.
6. The indolo spirofluorene organic compound according to any one of claims 1 to 5, wherein the indolo spirofluorene organic compound is any one of the following compounds:
Figure FDA0003372840830000031
Figure FDA0003372840830000041
Figure FDA0003372840830000051
7. a light-emitting layer comprising the indolo spirofluorene organic compound according to any one of claims 1 to 6.
8. A hole transport layer comprising the indolo spirofluorene organic compound according to any one of claims 1 to 6.
9. An organic electroluminescent device comprising the indolo spirofluorene organic compound according to any one of claims 1 to 6;
preferably, the organic electroluminescent device comprises an anode, a cathode and an organic thin film layer disposed between the anode and the cathode, the organic thin film layer comprising the indolo spirofluorene organic compound according to any one of claims 1 to 6;
preferably, the organic thin film layer comprises a hole transport layer comprising the indolo spirofluorene-based organic compound according to any one of claims 1 to 6;
preferably, the organic thin film layer includes a light-emitting layer including the indolo spirofluorene-based organic compound according to any one of claims 1 to 6;
preferably, the indolo spirofluorene organic compound is used as a phosphorescent host material of a light-emitting layer.
10. A display device characterized by comprising the organic electroluminescent device according to claim 9.
CN202111406006.5A 2021-11-24 2021-11-24 Indolo spirofluorene organic compound, organic electroluminescent device and display device Pending CN113979920A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100003624A (en) * 2008-07-01 2010-01-11 덕산하이메탈(주) Novel condensed carbazole derivatives and organic electroluminescent device comprising same
CN106207000A (en) * 2015-05-27 2016-12-07 三星显示有限公司 Organic luminescent device
CN108922987A (en) * 2018-06-21 2018-11-30 赵东敏 Biindolyl class material, organic electroluminescence device and display device
CN110964021A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with fluorene as core, preparation method and application thereof
CN113620860A (en) * 2020-12-14 2021-11-09 阜阳欣奕华材料科技有限公司 Organic electroluminescent compound and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100003624A (en) * 2008-07-01 2010-01-11 덕산하이메탈(주) Novel condensed carbazole derivatives and organic electroluminescent device comprising same
CN106207000A (en) * 2015-05-27 2016-12-07 三星显示有限公司 Organic luminescent device
CN108922987A (en) * 2018-06-21 2018-11-30 赵东敏 Biindolyl class material, organic electroluminescence device and display device
CN110964021A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with fluorene as core, preparation method and application thereof
CN113620860A (en) * 2020-12-14 2021-11-09 阜阳欣奕华材料科技有限公司 Organic electroluminescent compound and preparation method and application thereof

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