CN108250213A - A kind of preparation and its application of novel OLED electron transport materials - Google Patents

A kind of preparation and its application of novel OLED electron transport materials Download PDF

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CN108250213A
CN108250213A CN201711427913.1A CN201711427913A CN108250213A CN 108250213 A CN108250213 A CN 108250213A CN 201711427913 A CN201711427913 A CN 201711427913A CN 108250213 A CN108250213 A CN 108250213A
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electron transport
transport material
layer
aromatic
electron
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张学衡
张海建
付文岗
迟鹏利
沈清
孙宝林
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Valiant Co Ltd
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Abstract

The invention discloses a kind of novel OLED electron transport materials preparation method and applications of the dissymmetrical structure containing benzoxazine and quinoxaline group, belong to technical field of organic electroluminescence.It is with structure shown below：Wherein, Ar is the aromatic group containing substituent group or without substituent group, and R is the aromatic substituent different from benzoxazine and quinoxaline group.The invention also discloses the preparation method and applications of above-mentioned OLED material.The OLED material of the present invention can meet high efficiency and high stability simultaneously, which is applied in organic electroluminescence device, can significantly improve the performance of device.

Description

A kind of preparation and its application of novel OLED electron transport materials
Technical field
The present invention relates to a kind of novel OLED electron transport materials and its application in organic electroluminescence device, specifically It is related to centered on aryl, the small molecule OLED materials and the material of the dissymmetrical structure containing benzoxazine and quinoxaline group Expect the application in organic electroluminescence device.
Background technology
In recent years, Organic Light Emitting Diode (organic light emitting diode, OLED) is as non-both at home and abroad Often popular emerging flat-panel screens product.Compared with traditional liquid crystal, organic light emitting diode (OLED) has self-luminous, extensively regards Fast response time, many advantages, such as Flexible Displays can be achieved in angle, this becomes the most advantageous competition of next-generation display technology Person is greatly paid close attention to by people.
At present, the performance of green light and red light material is very outstanding, can reach the requirement of commercialization, and blue light material Research it is then relatively weak, this also restricts the development of the full-color displays of OLED to shine based on red green blue tricolor.Generally For, since blue light material has wider band gap, it is difficult to meet requirement of the blue light material to high efficiency and high color purity simultaneously. The balance in terms of the two how is carried out, becomes the key for developing outstanding blue light material.
Good electron transport material can be obviously improved the performance of organic electroluminescence device.At present, OLED frequently with Electron transport material (such as Alq3, TPBi) electron mobility be not very good (10-5-10-6cm2/Vs).Although it develops Go out many electron transport materials applied to electroluminescent device, but the electricity of stability and high electron mobility can be had both simultaneously Sub- transmission material, which is not much, sees.
Invention content
The technical problems to be solved by the invention are to provide one kind, for the electron-transport material in organic electroluminescence device The compound of material can be effectively improved the efficiency of device.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of electron transport material, concrete structure such as 1 institute of formula Show：
Wherein, Ar is the aromatic group containing substituent group or without substituent group, and R is different from benzoxazine and quinoxalinyl The aromatic substituent of group.
Further, Ar be carbon atom number be 5~25 aromatic condensed ring, aromatic heterocycle or aromatic condensed ring containing substituent group, Aromatic heterocycle；The aromatic condensed ring, nitrogenous aromatic heterocycle or aromatic condensed ring, nitrogenous aromatic heterocycle containing substituent group that R is 5~25.
Further, between benzoxazine and quinoxaline group and phenyl link position can be, (formula 2) is aligned：
Further, Ar is with any one in lower structure：
Further, R is with any one in lower structure：
Electron transport material of the present invention can be prepared by C-C coupling reactions, the schematic diagram of specific synthetic route It is as follows：
Wherein, Ar is the aromatic group containing substituent group or without substituent group, and R is different from benzoxazine and quinoxalinyl The aromatic substituent of group.
The present invention also provides the applications that above-mentioned electron transport material is used for organic electroluminescence device.Prepared Organic Electricity Electroluminescence device generally comprises ITO (tin indium oxide) Conducting Glass (anode) being sequentially overlapped, hole injection layer (HAT- CN), hole transmission layer (NPB), luminescent layer (CBP:6%wt Ir (ppy)3), electron transfer layer, electron injecting layer (LiF) and the moon Pole layer (Al).All functional layers use vacuum evaporation process.The molecule knot of some used organic compounds in the device Structure formula is as follows：
The beneficial effects of the invention are as follows：
The OLED material of the present invention is specifically related to centered on aryl, and side, which connects, contains benzoxazine and quinoxaline group, and one The small molecule OLED materials of the dissymmetrical structure of the other groups with electronic transmission performance of side connection, have good film forming Property；Containing big rigid radical in molecule, there is high thermal stability.It is applied in OLED device as electron transport material, Good device performance can be obtained, relatively low opens bright voltage；Meanwhile current efficiency, power efficiency and the outer quantum effect of device Rate is greatly improved.It is possible thereby to it learns：Organic photoelectrical material provided by the invention has good application in OLED Effect has good industrialization prospect.
Description of the drawings
Fig. 1 is the structure diagram of the organic electroluminescence device prepared by the present invention, by lower floor to upper strata, is followed successively by ITO Conducting Glass (101), hole injection layer (102), hole transmission layer (103), luminescent layer (104), electron transfer layer (105), electron injecting layer (106) and cathode layer (107), wherein, electron transfer layer (105) is related to of the present invention organic Electroluminescent material.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
Compound prepares embodiment：
The preparation of intermediate C
Under nitrogen protection, by 12H- benzos [5,6] [Isosorbide-5-Nitrae] oxazines simultaneously [2,3-b] quinoxaline (23.5g, 0.1mol) and Bromo-iodobenzene (28.3g, 0.1mol) is put into 200mL dimethylbenzene, in backward system add in sodium tert-butoxide (19.2g, 0.2mol), palladium (22.4mg, 1mmol), tri-tert-butylphosphine tetrafluoroborate (58mg, 2mmol).Back flow reaction 12h.Instead It should finish, directly be filtered after being cooled to room temperature, after filtrate is using washing, liquid separation, decompression obtains crude product after deviating from dimethylbenzene.Crude product Yellow solid, as intermediate C, yield 40% are recrystallized to give using toluene/dichloroethanes.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C20H12BrN3O, theoretical value 390.2328, test value 390.2410.Elemental analysis (C20H12BrN3O), theoretical value C：61.56 H：3.10 N：10.77 Br：20.48 measured value C： 60.80 H：3.15 N：10.80 Br：20.51.
The preparation of intermediate D
Under nitrogen protection, by 12H- benzos [5,6] [Isosorbide-5-Nitrae] oxazines simultaneously [2,3-b] quinoxaline (23.5g, 0.1mol) and Between bromo-iodobenzene (28.3g, 0.1mol) put into 200mL dimethylbenzene, in backward system add in sodium tert-butoxide (19.2g, 0.2mol), palladium (22.4mg, 1mmol), tri-tert-butylphosphine tetrafluoroborate (58mg, 2mmol).Back flow reaction 12h.Instead It should finish, directly be filtered after being cooled to room temperature, after filtrate is using washing, liquid separation, decompression obtains crude product after deviating from dimethylbenzene.Crude product Yellow solid, as intermediate D, yield 42% are recrystallized to give using toluene/dichloroethanes.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C20H12BrN3O, theoretical value 390.2328, test value 390.2412.Elemental analysis (C20H12BrN3O), theoretical value C：61.56 H：3.10 N：10.77 Br：20.48 measured value C： 60.78 H：3.16 N：10.76 Br：20.55.
The preparation of 1 electron transport material C01 of embodiment
Under nitrogen protection, intermediate C (3.9g, 0.01mol) and -1 phenylboric acid of 4- naphthalenes (2.98g, 0.012mol) are added Enter into 100mL toluene, then put into catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System, which is warming up to, to be refluxed 8 hours, is naturally cooling to liquid separation after room temperature, and revolving obtains crude product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:5 purification ＆ isolations, obtain buff powder, by gained powder End obtains compound C01, yield 52% using the further sublimation purification of chemical gas-phase deposition system, 360 DEG C of sublimation temperature.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C36H23N3O, theoretical value 513.5873, test value 513.5870. Elemental analysis (C36H23N3O), theoretical value C：84.19 H：4.51 N：8.18, measured value C：84.20 H：4.50 N：8.22.
The preparation of 2 electron transport material C02 of embodiment
Under nitrogen protection, by intermediate C (3.9g, 0.01mol) and (10- (1- naphthalenes) anthryl -9- bases) boric acid (4.18g, It 0.012mmol) is added in 100mL toluene, then puts into catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System, which is warming up to, to be refluxed 8 hours, is naturally cooling to liquid separation after room temperature, and revolving obtains thick Product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:4 purification ＆ isolations, obtain yellow powder, by gained powder Using the further sublimation purification of chemical gas-phase deposition system, 370 DEG C of sublimation temperature obtains compound C02, yield 50%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C44H27N3O, theoretical value 613.7047, test value 613.7050. Elemental analysis (C44H27N3O), theoretical value C：86.11 H：4.43 N：6.85, measured value C：86.20 H：4.46 N：6.90.
The preparation of 3 electron transport material C03 of embodiment
Under nitrogen protection, by intermediate C (3.9g, 0.01mol) and 4,4'- (5- (4,4,5,5- tetramethyls -1,3,2- dioxies Miscellaneous penta ring -2- bases of boron) -1,3- phenylenes) two pyridines (4.3g, 0.012mmol) are added in 100mL toluene, and then input is urged Agent tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System is warming up to reflux and stirs It mixes 10 hours, is naturally cooling to liquid separation after room temperature, revolving obtains crude product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:6 purification ＆ isolations, obtain yellow powder, by gained powder Using the further sublimation purification of chemical gas-phase deposition system, 350 DEG C of sublimation temperature obtains compound C03, yield 48%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C36H23N5O, theoretical value 541.6007, test value 541.6001. Elemental analysis (C36H23N5O), theoretical value C：79.83 H：4.28 N：12.93 measured value C：79.90 H：4.32 N：12.88.
The preparation of 4 electron transport material C04 of embodiment
Under nitrogen protection, by intermediate C (3.9g, 0.01mol) and (4- (1- phenyl) -1H- benzos [d] imidazoles -2- bases) benzene Base) boric acid (3.77g, 0.012mmol) is added in 100mL toluene, then put into catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System, which is warming up to, to be refluxed 8 hours, is naturally cooling to room temperature Liquid separation afterwards, revolving obtain crude product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:4 purification ＆ isolations, obtain yellow powder, by gained powder Using the further sublimation purification of chemical gas-phase deposition system, 360 DEG C of sublimation temperature obtains compound C04, yield 48%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C39H25N5O, theoretical value 579.6487, test value 579.6480. Elemental analysis (C39H25N5O), theoretical value C：80.81 H：4.35 N：12.08 measured value C：80.62 H：4.30 N：12.11.
The preparation of 5 electron transport material C05 of embodiment
Under nitrogen protection, by intermediate C (3.9g, 0.01mol) and 2,4- diphenyl -6- (3- (4,4,5,5- tetramethyl -1, 3,2- dioxa boron, penta ring -2- bases) phenyl) -1,3,5-triazines (5.22g, 0.012mmol) is added in 100mL toluene, then Put into catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System is warming up to It is refluxed 10 hours, is naturally cooling to liquid separation after room temperature, revolving obtains crude product.
Crude product is chromatographed with neutral alumina, eluent VN-hexane：VChloroform=1:5 purification ＆ isolations, obtain yellow powder, by gained Powder uses the further sublimation purification of chemical gas-phase deposition system, and 370 DEG C of sublimation temperature obtains compound C05, yield 46%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C41H26N6O, theoretical value 618.6847, test value 618.6851. Elemental analysis (C41H26N6O), theoretical value C：79.59 H：4.24 N：13.58 measured value C：79.62 H：4.26 N：13.62.
The preparation of 6 electron transport material C06 of embodiment
Under nitrogen protection, by intermediate C (3.9g, 0.01mol) and 4- (4- (4,4,5,5- tetramethyls -1,3,2- dioxa boron Penta ring -2- bases) phenyl) -1,10- ferrosins (4.59g, 0.012mmol) are added in 100mL toluene, then put into catalyst Tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System, which is warming up to, is refluxed 10 Hour, liquid separation after room temperature is naturally cooling to, revolving obtains crude product.
By crude product neutral alumina column chromatography, eluent VN-hexane：VChloroform=1:5 purification ＆ isolations, obtain yellow powder, by institute Powder is obtained using the further sublimation purification of chemical gas-phase deposition system, 360 DEG C of sublimation temperature obtains compound C06, yield 50%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C38H23N5O, theoretical value 565.6221, test value 565.6218. Elemental analysis (C38H23N5O), theoretical value C：80.69 H：4.10 N：12.38 measured value C：80.20 H：4.21 N：12.30.
The preparation of 7 electron transport material C07 of embodiment
Under nitrogen protection, by intermediate D (3.9g, 0.01mol) and 4- (4- (9,9- dimethyl -7- (4,4,5,5- tetramethyls - 1,3,2- dioxa boron, penta ring -2- bases) -9H- fluorenes -2- bases) phenyl) pyridine (5.68g, 0.012mmol) is added to 100mL toluene In, then put into catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.Body System, which is warming up to, to be refluxed 10 hours, is naturally cooling to liquid separation after room temperature, and revolving obtains crude product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:4 purification ＆ isolations, obtain yellow powder, by gained powder Using the further sublimation purification of chemical gas-phase deposition system, 360 DEG C of sublimation temperature obtains compound C07, yield 48%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C46H32N4O, theoretical value 656.7725, test value 656.7720. Elemental analysis (C46H32N4O), theoretical value C：84.12 H：4.91 N：8.53, measured value C：84.10 H：4.85 N：8.54.
The preparation of 8 electron transport material C08 of embodiment
Under nitrogen protection, by intermediate D (3.9g, 0.01mol) and 4,4,5,5- tetramethyl -2- (7- (naphthalene -1- bases) -9, 9- diphenyl -9H- fluorenes -2- bases) -1,3,2- dioxa boron, penta ring (6.84g, 0.012mmol) is added in 100mL toluene, so Catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution is put into afterwards.System heats up To being refluxed 10 hours, liquid separation after room temperature is naturally cooling to, revolving obtains crude product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:5 purification ＆ isolations, obtain yellow powder, by gained powder Using the further sublimation purification of chemical gas-phase deposition system, 360 DEG C of sublimation temperature obtains compound C08, yield 46%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C45H31N3O, theoretical value 629.7471, test value 629.7468. Elemental analysis (C45H31N3O), theoretical value C：85.83 H：4.96 N：6.67, measured value C：85.79 H：4.92 N：6.70.
The preparation of 9 electron transport material C09 of embodiment
Under nitrogen protection, by intermediate D (3.9g, 0.01mol) and 3- (7- (4,4,5,5- tetramethyls -1,3,2- dioxa boron Penta ring -2- bases) dibenzo [b, d] furans -4- bases) pyridine (4.45g, 0.012mmol) is added in 100mL toluene, then throws Enter catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System is warming up to back Stream stirring 10 hours, is naturally cooling to liquid separation after room temperature, and revolving obtains crude product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:4 purification ＆ isolations, obtain yellow powder, by gained powder Using the further sublimation purification of chemical gas-phase deposition system, 350 DEG C of sublimation temperature obtains compound C09, yield 50%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C37H22N4O2, theoretical value 554.5962, test value 554.5964. Elemental analysis (C37H22N4O2), theoretical value C：80.13 H：4.00 N：10.10 measured value C：80.05 H：4.05 N：10.12.
The preparation of 10 electron transport material C10 of embodiment
Under nitrogen protection, by intermediate D (3.9g, 0.01mol) and 4- (naphthalene -1- bases) -1- (4,4,5,5- tetramethyl -1, 3,2- dioxa boron, penta ring -2- bases) isoquinolin (4.57g, 0.012mmol) is added in 100mL toluene, then put into catalyst Tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System, which is warming up to, is refluxed 12 Hour, liquid separation after room temperature is naturally cooling to, revolving obtains crude product.
By crude product silica gel column chromatography, eluent VN-hexane：VChloroform=1:4 purification ＆ isolations, obtain yellow powder, by gained powder Using the further sublimation purification of chemical gas-phase deposition system, 360 DEG C of sublimation temperature obtains compound C10, yield 45%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C39H24N4O, theoretical value 564.6341, test value 564.6343. Elemental analysis (C39H24N4O), theoretical value C：82.96 H：4.28 N：9.92, measured value C：82.90 H：4.30 N：9.96.
The preparation of 11 electron transport material C11 of embodiment
Under nitrogen protection, by intermediate D (4.01g, 0.01mol) and 4'- (4- (4,4,5,5- tetramethyls -1,3,2- dioxas Penta ring -2- bases of boron) phenyl) -3,2':6', 3 "-terpyridyl (5.22g, 0.012mmol) are added in 100mL toluene, then Put into catalyst tetra-triphenylphosphine palladium (0.12g, 0.1mmol) and potassium carbonate (4.14g, 0.03mol) aqueous solution.System is warming up to It is refluxed 12 hours, is naturally cooling to liquid separation after room temperature, revolving obtains crude product.
By crude product neutral alumina column chromatography, eluent VN-hexane：VChloroform=1:4 purification ＆ isolations, obtain yellow powder, by institute Powder is obtained using the further sublimation purification of chemical gas-phase deposition system, 360 DEG C of sublimation temperature obtains compound C11, yield 40%.
High resolution mass spectrum, ESI sources, positive ion mode, molecular formula C41H26N6O, theoretical value 618.6847, test value 618.6850. Elemental analysis C41H26N6O), theoretical value C：79.59 H：4.24 N：13.58 measured value C：79.62 H：4.20 N：13.65.
Organic electroluminescence device embodiment：
The present invention chooses compound C01, compound C02, compound C03, compound C04, compound C05, compound 06, chemical combination Object 07, compound 07, compound 08, compound 09, compound 10, compound 11 make organic electroluminescence device, and select Commercialized electron transport material TPBI is as a comparison case.
It should be appreciated that device implementation process with as a result, being intended merely to preferably explain the present invention, not limitation of the present invention.
Application examples 1
Applications of the compound C01 in organic electroluminescence device：
A) ITO (tin indium oxide) glass is cleaned：It is small with deionized water, acetone, absolute ethyl alcohol ultrasonic cleaning ito glass each 2 respectively When, then handled 10 minutes in plasma cleaner；
B) the vacuum evaporation hole injection layer HAT-CN on anode ito glass, thickness 10nm；
C) vacuum evaporation or solution film forming hole transmission layer NPB, thickness 50nm on anode ito glass；
D) on hole transmission layer NPB, vacuum evaporation luminescent layer CBP:6%wt Ir (ppy)3, thickness 30nm；
E) in luminescent layer CBP:6%wt Ir (ppy)3On, vacuum evaporation electron transfer layer compound C01, thickness 50nm；
F) on electron transfer layer compound C01, vacuum evaporation electron injecting layer LiF, thickness 1nm；
G) on electron injecting layer LiF, vacuum evaporation cathode Al, thickness 80nm.
The structure of device one is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C01(50nm)/LiF(1nm)/Al(80nm).During vacuum evaporation, pressure<2.0×10-4Pa, using compound C01 as device The electron transport material of part one, the test result of obtained device are shown in Table 1.
Application examples 2
The structure of device two is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C02(50nm)/LiF(1nm)/Al(80nm).Using compound C02 as the electron transport material of device two, the survey of obtained device Test result is shown in Table 1.
Application examples 3
The structure of device three is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C03(50nm)/LiF(1nm)/Al(80nm).Using compound C03 as the electron transport material of device three, the survey of obtained device Test result is shown in Table 1.
Application examples 4
The structure of device four is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C04(50nm)/LiF(1nm)/Al(80nm).Using compound C04 as the electron transport material of device four, the survey of obtained device Test result is shown in Table 1.
Application examples 5
The structure of device five is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C05(50nm)/LiF(1nm)/Al(80nm).Using compound C05 as the electron transport material of device five, the survey of obtained device Test result is shown in Table 1.
Application examples 6
The structure of device six is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C06(50nm)/LiF(1nm)/Al(80nm).Using compound C06 as the electron transport material of device six, the survey of obtained device Test result is shown in Table 1.
Application examples 7
The structure of device seven is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C07(50nm)/LiF(1nm)/Al(80nm).Using compound C07 as the electron transport material of device seven, the survey of obtained device Test result is shown in Table 1.
Application examples 8
The structure of device eight is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C08(50nm)/LiF(1nm)/Al(80nm).Using compound C08 as the electron transport material of device eight, the survey of obtained device Test result is shown in Table 1.
Application examples 9
The structure of device nine is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C09(50nm)/LiF(1nm)/Al(80nm).Using compound C09 as the electron transport material of device nine, the survey of obtained device Test result is shown in Table 1.
Application examples 10
The structure of device ten is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/compound C10(50nm)/LiF(1nm)/Al(80nm).Using compound C10 as the electron transport material of device ten, the survey of obtained device Test result is shown in Table 1.
Application examples 11
The structure of device 11 is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/chemical combination Object C11 (50nm)/LiF (1nm)/Al (80nm).Using compound C11 as the electron transport material of device 11, obtained device Test result be shown in Table 1.
Comparative example
The structure of device 12 is ITO/HAT-CN (10nm)/NPB (50nm)/CBP:6%wt Ir (ppy)3(30nm)/TPBI (50nm)/LiF (1nm)/Al (80nm), is shown in using TPBI as the electron transport material of comparative example, the test result of obtained device Shown in table 1.
1 device one of table is to 12 photooptical data table of device
The foregoing is merely the embodiment of the present invention, are not limitation of the present invention.The present invention is intended to provide one kind contains There is the electroluminescent organic material of benzoxazine and quinoxaline structure, with the OLED device that material provided by the present invention makes, Device architecture and performance have the space further promoted, the emitting layer material for other colors of such as arranging in pairs or groups, and make red device or indigo plant Optical device adds other functional layers, carrys out further lifter using other hole mobile materials or in the device structure Part performance etc., it is similar to improve all it should be understood that belonging to the protection category of the present invention.

Claims (8)

1. a kind of electron transport material, which is characterized in that the structural formula of the electron transport material is as follows：
Wherein, Ar is the aromatic group containing substituent group or without substituent group, and R is different from benzoxazine and quinoxaline group Aromatic substituent.
2. electron transport material according to claim 1, which is characterized in that the Ar is the virtue that carbon atom number is 5~25 Fragrant condensed ring, aromatic heterocycle or aromatic condensed ring, aromatic heterocycle containing substituent group；R be 5~25 aromatic condensed ring, nitrogenous fragrance it is miscellaneous Ring or aromatic condensed ring, nitrogenous aromatic heterocycle containing substituent group.
Between 3. electron transport material according to claim 1, benzoxazine and quinoxaline group and phenyl link position are Position or contraposition (formula 2)：
4. electron transport material according to claim 2, it is characterised in that Ar is with any one in lower structure：
5. electron transport material according to claim 2, it is characterised in that R is with any one in lower structure：
6. a kind of application of novel OLED material, which is characterized in that field of organic electroluminescence is used in, as electron-transport Material or hole barrier materials use.
7. a kind of OLED electroluminescent devices material therefor, it is characterised in that including containing in Claims 1 to 55 described in any one Electron transport material.
8. a kind of electroluminescent device including transparent substrate layer, transparent electrode layer, hole injection layer, hole transmission layer, shines Layer, electron transfer layer, electron injecting layer, cathode reflection electrode layer, which is characterized in that in the luminescent layer and electron transfer layer In at least one layer containing described in any one in Claims 1 to 5 with electron transport material.
CN201711427913.1A 2017-12-26 2017-12-26 A kind of preparation and its application of novel OLED electron transport materials Withdrawn CN108250213A (en)

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PL217059B1 (en) * 2012-02-13 2014-06-30 Politechnika Łódzka Compounds, derivatives of 12-phenyl-12H-quinoxaline-[2,3-b] [1,4] benzothiazine and the process for their preparation

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CN1612058A (en) * 2003-10-31 2005-05-04 三星电子株式会社 Organophotoreceptor with charge transport material with a hydrazone group linked to a heterocyclic group
US20090026928A1 (en) * 2007-07-24 2009-01-29 Samsung Electronics Co., Ltd. Phenylphenoxazine or phenylphenothiazine- based compound and organic electroluminescent device using the same
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