CN114507225B - N-containing heterocyclic compound and application thereof in organic light-emitting device and panel - Google Patents

N-containing heterocyclic compound and application thereof in organic light-emitting device and panel Download PDF

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CN114507225B
CN114507225B CN202210211743.8A CN202210211743A CN114507225B CN 114507225 B CN114507225 B CN 114507225B CN 202210211743 A CN202210211743 A CN 202210211743A CN 114507225 B CN114507225 B CN 114507225B
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heterocyclic compound
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CN114507225A (en
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陆婷婷
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Shanghai Tianma Microelectronics Co Ltd
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Abstract

The invention provides an N-containing heterocyclic compound, which has a structure shown in a formula I. The N-containing heterocyclic compound provided by the invention has proper HOMO and LUMO values, can reduce injection potential barrier, effectively balance carrier transmission, has high electron mobility, excellent stability and film forming property, is beneficial to improving electron transmission rate, balancing electron and hole injection, improving luminous efficiency and service life of a device, and reducing operating voltage of the device.

Description

N-containing heterocyclic compound and application thereof in organic light-emitting device and panel
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to an N-containing heterocyclic compound and application thereof in organic light-emitting devices and panels.
Background
The electron transport material used in conventional electroluminescent devices is Alq3, but the electron mobility of Alq3 is relatively low (about l0 -6cm2/Vs), making the carrier transport of the device unbalanced. With commercialization of electroluminescent devices, ETL materials having higher electron mobility and better usability are desired, and in this field, researchers have made a lot of research.
The design and development are stable and efficient, can have high electron mobility and high glass transition temperature at the same time, and the electron transport material and/or electron injection material which are effectively doped with the metal Yb or Liq reduces the threshold voltage, improves the device efficiency, prolongs the device service life, and has important practical application value.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an N-containing heterocyclic compound and application thereof in organic light-emitting devices and panels, wherein the prepared N-containing heterocyclic compound can be used as an electron transport material to improve the light-emitting efficiency and the service life of the devices.
The invention provides an N-containing heterocyclic compound, which has a structure shown in a formula I:
Wherein X is selected from O, S, NR 1 or CR 2R3;
Z 1、Z2 and Z 3 are independently selected from N or C and contain at least one N;
L l and L 2 are the same or different and are each independently selected from substituted or unsubstituted arylene or heteroarylene; the substituents of the arylene and heteroarylene are independently selected from arylene or heteroarylene;
Ar 1、Ar2 and Ar 3 are each independently selected from substituted or unsubstituted aryl or heteroaryl;
R 1、R2 and R 3 are each independently selected from H, substituted or unsubstituted aryl or heteroaryl.
The invention provides a display panel, which comprises an organic light-emitting device, wherein the organic light-emitting device comprises an anode, a cathode and an organic thin film layer positioned between the anode and the cathode, the organic thin film layer comprises an electron transport layer, and the electron transport layer contains at least one N-containing heterocyclic compound.
The invention provides a display device which comprises the display panel.
Compared with the prior art, the invention provides an N-containing heterocyclic compound which has a structure shown in a formula I. The N-containing heterocyclic compound provided by the invention has proper HOMO and LUMO values, can reduce injection potential barrier, effectively balance carrier transmission, has high electron mobility, excellent stability and film forming property, is beneficial to improving electron transmission rate, balancing electron and hole injection, improving luminous efficiency and service life of a device, and reducing operating voltage of the device.
Detailed Description
The invention provides an N-containing heterocyclic compound, which has a structure shown in a formula I:
Wherein X is selected from O, S, NR 1 or CR 2R3;
Z 1、Z2 and Z 3 are independently selected from N or C and contain at least one N;
L l and L 2 are the same or different and are each independently selected from substituted or unsubstituted arylene or heteroarylene; the substituents of the arylene and heteroarylene are independently selected from arylene or heteroarylene;
Ar 1、Ar2 and Ar 3 are each independently selected from substituted or unsubstituted aryl or heteroaryl;
R 1、R2 and R 3 are each independently selected from H, substituted or unsubstituted aryl or heteroaryl.
Optionally, any two of Z 1、Z2 and Z 3 are N, or Z 1、Z2 and Z 3 are both N.
Optionally, L l and L 2 are the same or different and are each independently selected from any one of the following:
a. A substituted or unsubstituted monocyclic arylene group;
b. A substituted or unsubstituted monocyclic heteroarylene group containing 1 to 3N atoms;
c. a substituted or unsubstituted condensed ring group formed by the condensation of a and/or b;
The total number of a and/or b contained in the condensed ring group is 2-3;
The substituents of a, b and c are independently selected from monocyclic aryl, monocyclic heteroaryl, fused ring groups formed by the condensation of monocyclic aryl and/or monocyclic heteroaryl.
Optionally, the monocyclic arylene is phenylene.
Optionally, the monocyclic heteroarylene group containing 1 to 3N atoms is a pyridylene group, a pyrazinylene group, a pyrimidinylene group, a pyridazinylene group, a1, 2, 3-triazinylene group, a1, 3, 5-triazinylene group or a1, 3, 4-triazinylene group.
Alternatively, the L l and L 2 are the same or different and are each independently selected from substituted or unsubstituted phenylene, pyridylene, pyrazinylene, pyrimidinylene, pyridazinylene, 1,2, 3-triazinylene, 1,3, 5-triazinylene, 1,3, 4-triazinylene, naphthylene, anthracylene, phenanthrylene, quinolinylene, isoquinolinyl, quinoxalinylene, 1, 5-naphthyridinyl or 1, 6-naphthyridinyl;
The substituents of the above groups are selected from phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, carbazolyl, benzodifuranyl, benzodithiophene or fluorenyl.
Optionally, each of Ar 1、Ar2 and Ar 3 is independently selected from any one of the following:
a. A substituted or unsubstituted monocyclic aryl group;
b. a substituted or unsubstituted monocyclic heteroaryl group containing 1 to 3N atoms;
c. a substituted or unsubstituted condensed ring group formed by the condensation of a and/or b;
The total number of a and/or b contained in the condensed ring group is 2-3;
The substituents of a, b and c are independently selected from monocyclic aryl, monocyclic heteroaryl, fused ring groups formed by the condensation of monocyclic aryl and/or monocyclic heteroaryl.
Optionally, the monocyclic arylene is phenylene.
Optionally, the monocyclic heteroarylene group containing 1 to 3N atoms is a pyridylene group, a pyrazinylene group, a pyrimidinylene group, a pyridazinylene group, a1, 2, 3-triazinylene group, a1, 3, 5-triazinylene group or a1, 3, 4-triazinylene group.
Alternatively, ar 1、Ar2 and Ar 3 are each independently selected from phenyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, naphthyl, anthracenyl, phenanthryl, quinolinyl, isoquinolinyl, quinoxalinyl, 1, 5-naphthyridinyl, or 1, 6-naphthyridinyl.
Optionally, each of R 1、R2 and R 3 is independently selected from H or any of the following:
a. A substituted or unsubstituted monocyclic aryl group;
b. a substituted or unsubstituted monocyclic heteroaryl group containing 1 to 3N atoms;
c. a substituted or unsubstituted condensed ring group formed by the condensation of a and/or b;
The total number of a and/or b contained in the condensed ring group is 2-3;
The substituents of a, b and c are independently selected from monocyclic aryl, monocyclic heteroaryl, fused ring groups formed by the condensation of monocyclic aryl and/or monocyclic heteroaryl.
Optionally, the monocyclic arylene is phenylene.
Optionally, the monocyclic heteroarylene group containing 1 to 3N atoms is a pyridylene group, a pyrazinylene group, a pyrimidinylene group, a pyridazinylene group, a1, 2, 3-triazinylene group, a1, 3, 5-triazinylene group or a1, 3, 4-triazinylene group.
Alternatively, R 1、R2 and R 3 are each independently selected from H, phenyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, naphthyl, anthracenyl, phenanthryl, quinolinyl, isoquinolinyl, quinoxalinyl, 1, 5-naphthyridinyl or 1, 6-naphthyridinyl.
Optionally, the above-mentioned N-containing heterocyclic compound has any one of the following structures:
the N-containing heterocyclic compound provided by the invention can be used for an electron transport layer of an organic photoelectric device.
The invention provides a display panel, which comprises an organic light-emitting device, wherein the organic light-emitting device comprises an anode, a cathode and an organic thin film layer positioned between the anode and the cathode, the organic thin film layer comprises an electron transport layer, and the electron transport layer contains at least one N-containing heterocyclic compound.
The organic light-emitting device provided by the invention can be an organic light-emitting device well known to a person skilled in the art, and optionally comprises a substrate, an ITO anode, a first hole transport layer, a second hole transport layer, an electron blocking layer, a light-emitting layer, a first electron transport layer, a second electron transport layer, a cathode (magnesium-silver electrode, magnesium-silver mass ratio of 1:9) and a capping layer (CPL).
Alternatively, the anode material of the organic light-emitting device may be selected from metal-copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof; such as metal oxide-indium oxide, zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and the like; such as the conductive polymers polyaniline, polypyrrole, poly (3-methylthiophene), and the like, include materials known to be suitable as anodes in addition to facilitating hole injection materials and combinations thereof.
The cathode material of the organic light-emitting device can be selected from metal-aluminum, magnesium, silver, indium, tin, titanium and the like and alloys thereof; such as multi-layer metallic materials-LiF/Al, liO 2/Al、BaF2/Al, etc.; materials suitable for use as cathodes are also known in addition to the above materials that facilitate electron injection and combinations thereof.
The organic optoelectronic device, such as an organic light emitting device, has at least one light emitting layer (EML), and may further include other functional layers including a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL).
According to the invention, the organic light-emitting device is prepared according to the following method:
an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer.
Alternatively, the organic thin layer may be formed by known film forming methods such as evaporation, sputtering, spin coating, dipping, ion plating, and the like.
The invention provides a display device which comprises the display panel.
In the present invention, an organic light emitting device (OLED device) may be used in a display apparatus, wherein the organic light emitting display apparatus may be a mobile phone display screen, a computer display screen, a television display screen, a smart watch display screen, a smart car display panel, a VR or AR helmet display screen, display screens of various smart devices, or the like.
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1 preparation of substrate
Preparation of Sub1
To a 1L reaction vessel were charged mid1-1 (20 g,90.4 mmol), 4, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborane (27.8 g,180.8 mmol), dioxane (400 ml) and PdCl 2 (dtbpf) (5.92 g,9 mmol), reacted under nitrogen for 0.5h, then injected with K 3PO4 solution (0.576 g/ml,100 ml) and heated to 80℃overnight, and TCL was tracked until the starting material point disappeared. The reaction mixture was filtered through celite and the filtrate was concentrated to dryness. The residue was purified by column chromatography on silica gel eluting with ethyl acetate/petroleum ether (10%, v/v) to give mid1-2 (10 g, 65%).
250Ml of dimethyl sulfoxide, 2-iodoxybenzoic acid (28 g,100 mmol) and I 2 (25.4 g,100 mmol) were added to the reaction vessel, stirred at room temperature for 20min to dissolve, and then mid1-2 (8.5 g,50 mmol) and 10ml of glacial acetic acid were added, reacted at 70℃for 30 min, followed by rapid heating to 120℃for 12h, distillation under reduced pressure, removal of the solvent and isolation by column chromatography to give mid1-3 (4 g, 44%).
200Ml of ethanol, mid1-3 (36.2 g,200 mmol), NBS (5 g,440 mmol) and copper nitrate (3.75 g,20 mmol) were added in this order, stirred at room temperature for 0.5h, and then warmed to 50℃for 3h. The TCL tracks the reaction until the starting point disappears. The temperature was lowered to 20℃and the reaction solution was poured into 200ml of water and stirred for 2h. Suction filtration, stirring the filter cake at a water chamber temperature of 200ml for 1h, suction filtration and drying at 50 ℃ to obtain mid1-4 (37 g, 55%).
To a 2L two-necked flask were added mid1-4 (50 g,148 mmol) and methylene chloride (1L), and titanium tetrachloride (1M, 232 ml) was slowly dropped at 0℃to slowly drop dimethylamine borane complex (21.5 ml), followed by neutralization with sodium carbonate (1M) after 2 hours of reaction at 0 ℃. The reaction solution was extracted with dichloromethane and distilled water to obtain an organic layer. After drying, the mixture was concentrated under reduced pressure to give a red substance, and tert-butanol (34 g,300 mmol) was dissolved in dimethyl sulfoxide (250 ml), followed by stirring for 1 hour and then by slowly dropwise addition of methyl iodide (43 g,300 mmol), followed by stirring at 80℃for 12 hours. The organic layer was separated from the acetone, dried over magnesium sulfate and distilled under reduced pressure. The product sub1 (22 g, 43%) was obtained using a hexane silica gel column.
Preparation of Sub2
In a 1L reactor, bromobenzene (36 g,330 mmol) was dissolved in tetrahydrofuran (200L), followed by dropwise addition of butyllithium (2.5M, 154.4 ml) at a low temperature of-78℃and stirring for 2 hours. Then midl-4 (50 g,148 mmol) dissolved in tetrahydrofuran (300 ml) was slowly added dropwise to the reactor at-78℃and stirring was maintained at room temperature for 24 hours. After the reaction was completed, the sodium carbonate 1M solution was neutralized. After separation of the organic layer, tetrahydrofuran was removed, extracted twice with ethyl acetate and distilled water and dried. The mixture was placed under nitrogen and then benzene (11.1 g,45.2 mmol) and 570mL of dichloromethane were added. Boron trifluoride diethyl etherate (5.7 mL,45.2 mmol) dissolved in dichloromethane was slowly added dropwise. Stirring at normal temperature for 2 hours. The reaction was stopped with methanol and distilled water, the organics were extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the compound sub2 (14.51 g, 85%) was purified by column chromatography.
Preparation of Sub3
After 2-bromobiphenyl (54 g,232 mmol) was dissolved in tetrahydrofuran (200L) in a 1L reaction vessel, butyllithium (2.5M, 154.4 ml) was slowly added dropwise at a low temperature of-78℃and stirred for 2 hours. Then mid1-4 (50 g,148 mmol) dissolved in tetrahydrofuran (300 ml) was slowly dropped at-78℃and stirred at room temperature for 24 hours. After the reaction was completed, the sodium carbonate 1M solution was neutralized. The organic layer was separated, tetrahydrofuran was removed by rotary evaporation, extracted twice with ethyl acetate and distilled water and dried. Then, hydrochloric acid (10 ml) and acetic acid (350 ml) were added thereto, followed by stirring under reflux for 24 hours. The reaction solution was cooled at room temperature, and then the solid was filtered and washed several times with methanol. Product sub3 (28 g, 40%) was isolated using a hexane silica gel column.
Preparation of Sub4
Mid1-3 was replaced with mid4-1 and mid4-2 was prepared according to the same molar ratio used for mid 1-4.
To the reaction vessel were added mid4-2 (48.6 g,150 mmol), cs 2CO3 (48.9 g,150 mmol) and CuCl (1.19 g,12 mmol). To N-methylpyrrolidone (300 mL) were added acetylacetone (115 mL) and bromobenzene (31 g,120 mmol), and the reaction mixture was heated at 130℃for 18 hours under argon atmosphere. The suspension was cooled to ambient temperature. To the suspension was added saturated NaHCO 3 (aq) (1L). The mixture was filtered. The filtrate was washed with saturated NaHCO 3 (aq) (1L). The organic product was extracted with dichloromethane. The solvent was evaporated. Purification by flash column chromatography on silica gel using dichloromethane/methanol as eluent (v/v=40:1) afforded product sub4 (42 g, 70%).
Preparation of Sub5
The preparation method of Sub5 is basically identical to Sub4, except that bromobenzene used for preparing Sub4 is replaced by 2-bromodibenzofuran.
Preparation of Sub6
To the reactor was added mid6-1 (55 g, 247 mmol) and triethyl orthoformate (500 mL). The resulting mixture was refluxed for 4-8 hours until TLC showed complete consumption of starting material. The excess triethyl orthoformate was then removed under reduced pressure. Purification by flash column chromatography on silica gel using petroleum ether/ethyl acetate as eluent (v/v=20:1) afforded the product mid6-2 (40 g, 95%).
Sub6 was prepared by substituting mid1-3 for mid6-2 in the same molar ratio as used for mid 1-4.
Preparation of Sub7
Mid7-1 (35 g,97 mmol) was dissolved in tetrahydrofuran (250 ml), then 2-bromo-6-iodopyridine (30 g,106 mmol), tetraphenylphosphine palladium (4.3 g,3.72 mmol), K 2CO3 (52 g,372 mmol) and water were added and stirred at 100℃under reflux for 3 hours. When the reaction was completed, extraction was performed with ethyl acetate and water, and the organic layer was dried over anhydrous MgSO 4 and concentrated, and the resultant organic was separated and purified by a silica gel column, thereby obtaining mid7-2 (33 g, 88%).
Mid7-2 (10 g,25.8 mmol) was dissolved in DMF (150 ml) and then bis (pinacolato) diboron (10 g,35.3 mmol), pd (dppf) Cl 2 (1.3 g,1.77 mmol) and KOAc (23.5 g,170 mmol) were added and stirred at 130℃under reflux for 4 hours. When the reaction was completed, DMF was removed by distillation and extracted with CH 2Cl2 and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was subjected to a silica gel column and recrystallized to give mid7-3 (7 g, 62%).
Mid7-4 was prepared in a manner consistent with the preparation of mid7-2 by substituting 2-bromo-6-iodopyridine with 1-bromo-4-iodobenzene. Next mid7-2 is replaced with mid7-4 to prepare sub7 in a manner consistent with the preparation of mid 7-3.
Preparation of Sub8
Preparation of mid8-2 by replacing mid7-1 with mid8-1, 2-bromo-6-iodopyridine with 1-bromo-4-iodonaphthalene sub8 was prepared in the same manner as mid7-3 by replacing mid7-2 with mid8-2.
Preparation of Sub9
The preparation method of Sub9 is basically identical to Sub4, except that bromobenzene used for preparing Sub4 is replaced by 3-bromopyridine.
Preparation of Sub10
In a manner consistent with the preparation of mid7-2, mid10-1 was replaced with mid10-1 and mid7-1 was replaced with 7- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) benzoxazole to prepare mid10-2. Next, mid10-2 was replaced with mid10-2 to prepare mid10-3 in the same manner as mid 7-3. Mid10-4 and sub10 were prepared as well, replacing the corresponding reactants.
Preparation of E1
After the compound 2, 4-diphenyl-6- [4'- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine (10.0 g,19.6 mmol) and sub1 (7.0 g,19.9 mmol) were completely dissolved in 100ml of tetrahydrofuran under nitrogen atmosphere, the reaction was first carried out for half an hour, and tetrakis triphenylphosphine palladium (620 mg,0.537 mmol) was added thereto, followed by the addition of potassium carbonate (7.4 g,53.7 mmol) dissolved in 43ml of water, followed by heating and stirring for 7 hours. The reaction temperature was lowered to room temperature, the reaction was completed, and then the potassium carbonate solution was removed by filtration and the residue was washed twice with tetrahydrofuran and ethyl acetate to give sub1-1 (9.5 g, 74%).
The pinacol phenylborate (4.0 g,19.6 mmol) and sub1-1 (13.5 g,20.6 mmol) were completely dissolved in 100ml dimethyl sulfoxide under nitrogen atmosphere, and tetrakis triphenylphosphine palladium (620 mg,0.537 mmol) was added thereto for half an hour, followed by addition of potassium carbonate (7.4 g,53.7 mmol), followed by heating and stirring for 30 hours. The solvent was then distilled off under reduced pressure, and the solid was washed with water several times, dried and purified by sublimation to give E1 (9.5 g, 74%).
Preparation of E2
The preparation method of E2 is consistent with E1, and the same molar ratio is used for replacing sub1 with sub2 according to the preparation method of E1.
Preparation of E3
The preparation method of E3 is identical with that of E1, and according to the preparation method of E1, sub1 is replaced by sub2, 4-diphenyl-6- [4'- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine, sub 2-diphenyl-6- [4'- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -3-yl ] -1,3, 5-triazine and sub1-1 is replaced by sub 2-1.
Preparation of E4
The preparation method of E4 is consistent with E1, and according to the preparation method of E1, sub1 is replaced by sub2, 4-diphenyl-6- [4'- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine is replaced by sub7, and sub1-1 is replaced by sub4-1 by using the same molar ratio.
Preparation of E5
The preparation method of E5 is consistent with E1, and according to the preparation method of E1, the same molar ratio is used for replacing sub1 with sub3, and sub1-1 is replaced with sub 5-1.
Preparation of E6
The preparation method of E6 is consistent with E1, and according to the preparation method of E1, sub1 is replaced by sub2, 4-diphenyl-6- [4'- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine is replaced by sub8, and sub1-1 is replaced by sub6-1 by using the same molar ratio.
Preparation of E7
The preparation method of E7 is consistent with E1, and according to the preparation method of E1, the same molar ratio is used for replacing sub1 with sub4, and sub1-1 is replaced with sub 7-1.
Preparation of E8
The preparation method of E8 is consistent with E1, and according to the preparation method of E1, the same molar ratio is used for replacing sub1 with sub5, and sub1-1 is replaced with sub 8-1.
Preparation of E9
The preparation method of E9 is consistent with E1, and according to the preparation method of E1, the same molar ratio is used for replacing sub1 with sub4, and sub1-1 is replaced with sub 9-1.
Preparation of E10
The preparation method of E10 is consistent with E1, and according to the preparation method of E1, the same molar ratio is used for replacing sub1 with sub6, and sub1-1 is replaced with sub 10-1.
Preparation of E11
The preparation method of E11 is consistent with E1, and according to the preparation method of E1, sub1 is replaced by sub4,2, 4-diphenyl-6- [4'- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine is replaced by sub10, and sub1-1 is replaced by sub11-1 by using the same molar ratio.
The analysis of the time-of-flight mass spectrometry and elemental analysis of the compounds in the above examples by matrix assisted laser desorption ionization were confirmed and the results are shown in table 1 below.
TABLE 1
/>
Comparative example
To ITO (indium tin oxide)The glass substrate coated to have a thin film thickness is put into distilled water in which a detergent is dissolved, and washed with ultrasonic waves. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes. After the distilled water washing is completed, ultrasonic washing is performed by using solvents of isopropanol, acetone and methanol, and the obtained product is dried and then conveyed to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transferred to a vacuum vapor deposition machine.
On the above-prepared ITO transparent electrode, the following compound [ HI ] was usedAnd performing thermal vacuum evaporation to form a hole injection layer. On the hole injection layer, hexanitrile Hexaazabenzophenanthrene (HAT)/>, of the following chemical formula, is vacuum deposited in sequenceAnd the following compound [ HT ]/>And a hole transport layer is formed.
Next, the following compounds [ BH ] and [ BD ] were formed on the hole transport layer at a weight ratio of 25:1 and film thicknessVacuum vapor deposition is performed to form a light-emitting layer.
On the light-emitting layer, the following compounds [ ET ] and [ LiQ ] (8-hydroxyquinoline lithium, lithiumquinolate) were vacuum-evaporated at a weight ratio of 1:1 to give a light-emitting layerForm an electron injection and transport layer. On the electron injection and transport layer, lithium fluoride (LiF) is sequentially added as/>Thickness of aluminum to/>The thickness is evaporated to form a cathode.
In the process, the evaporation rate of the organic matters is maintained to be 0.4 toLithium fluoride maintenance of cathodeVapor deposition rate of aluminum maintenance/>During vapor deposition, the vacuum degree is maintained at 1×10 -7 to 5×10 -8 torr, thereby manufacturing an organic light emitting device.
/>
Experimental examples 1 to 11
An organic light-emitting device was manufactured in the same manner as in the comparative example except that the compound synthesized in example 1 was used instead of the compound [ ET ] according to the above comparative example.
For the organic light-emitting devices manufactured using the respective compounds as the electron transport layers in the above experimental examples and comparative examples, the driving voltage and the light-emitting efficiency were measured at a current density of 10mA/cm 2, and the time required for 95% relative to the initial luminance was measured at a current density of 20mA/cm 2 (LT 95). The results are shown in table 2 below.
TABLE 2
Name of the name Electron transport layer Voltage (V) Current efficiency (cd/A) LT95(h)
Comparative example ET 5.14 4.12 94
Experimental example 1 E1 5.10 4.02 105
Experimental example 2 E2 5.23 4.78 81
Experimental example 3 E3 5.20 4.77 90
Experimental example 4 E4 5.31 5.02 74
Experimental example 5 E5 5.24 4.69 80
Experimental example 6 E6 5.07 3.98 111
Experimental example 7 E7 4.98 4.09 124
Experimental example 8 E8 4.92 4.20 56
Experimental example 9 E9 5.04 4.13 92
Experimental example 10 E10 5.11 4.55 118
Experimental example 11 E11 5.15 4.02 48
As shown in table 1, the organic light emitting device prepared by the compound provided by the present invention shows excellent device characteristics compared with the comparative example, and it can be concluded that the compound provided by the present invention can adjust electron transport rate, thereby adjusting the balance of device carriers, showing a remarkable improvement in device performance (including light emitting efficiency and lifetime).
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (3)

1. An N-containing heterocyclic compound having any one of the following structures:
2. A display panel comprising an organic light-emitting device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode, the organic thin film layer comprising an electron transport layer comprising at least one N-containing heterocyclic compound according to claim 1.
3. A display device comprising the display panel of claim 2.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150076503A (en) * 2013-12-27 2015-07-07 희성소재 (주) Pyrimidine-based compound and organic light emitting device using the same
KR20160066440A (en) * 2014-12-02 2016-06-10 주식회사 두산 Organic light-emitting compound and organic electroluminescent device using the same
CN113563381A (en) * 2021-08-09 2021-10-29 上海天马有机发光显示技术有限公司 Organic electroluminescent compound and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150076503A (en) * 2013-12-27 2015-07-07 희성소재 (주) Pyrimidine-based compound and organic light emitting device using the same
KR20160066440A (en) * 2014-12-02 2016-06-10 주식회사 두산 Organic light-emitting compound and organic electroluminescent device using the same
CN113563381A (en) * 2021-08-09 2021-10-29 上海天马有机发光显示技术有限公司 Organic electroluminescent compound and application thereof

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