CN114507225A - 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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CN114507225A
CN114507225A CN202210211743.8A CN202210211743A CN114507225A CN 114507225 A CN114507225 A CN 114507225A CN 202210211743 A CN202210211743 A CN 202210211743A CN 114507225 A CN114507225 A CN 114507225A
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independently selected
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CN114507225B (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 appropriate HOMO and LUMO values, can reduce injection potential barrier, effectively balances the transmission of current carriers, has high electron mobility, excellent stability and film-forming property, is beneficial to improving the electron transmission rate, balancing the injection of electrons and holes, improving the luminous efficiency and the service life of a device, and reducing the 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 (approximately at l 0)-6cm2Vs) making the carrier transport of the device unbalanced. With the commercialization of electroluminescent devices, higher electron mobility and better performance of ETL materials are desired, and researchers have done a great deal of exploratory work in this area.
The electron transport material and/or the electron injection material which are stably and efficiently designed and developed, have high electron mobility and high glass transition temperature, are effectively doped with metal Yb or Liq, reduce threshold voltage, improve device efficiency, prolong device service life and have important practical application value.
Disclosure of Invention
In view of the above, the present invention provides a heterocyclic compound containing N and its application in organic light emitting devices and panels, and the prepared heterocyclic compound containing N can be used as an electron transport material to improve the light emitting efficiency and lifetime of the devices.
The invention provides an N-containing heterocyclic compound, which has a structure shown in a formula I:
Figure BDA0003531678900000011
wherein X is selected from O, S, NR1Or CR2R3；
Z1、Z2And Z3Independently selected from N or C, and containing at least one N;
Lland L2The same or different, and each is independently selected from substituted or unsubstituted arylene or heteroarylene; the substituents of the arylene and the heteroarylene are independently selected from arylene or heteroarylene;
Ar1、Ar2and Ar3Each independently selected from substituted or unsubstituted aryl or heteroaryl;
R1、R2and R3Each 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 of the N-containing heterocyclic compounds.
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 appropriate HOMO and LUMO values, can reduce injection potential barrier, effectively balances the transmission of current carriers, has high electron mobility, excellent stability and film-forming property, is beneficial to improving the electron transmission rate, balancing the injection of electrons and holes, improving the luminous efficiency and the service life of a device, and reducing the operating voltage of the device.
Detailed Description
The invention provides an N-containing heterocyclic compound, which has a structure shown in a formula I:
Figure BDA0003531678900000021
wherein X is selected from O, S, NR1Or CR2R3；
Z1、Z2And Z3Independently selected from N or C, and containing at least one N;
Lland L2The same or different, and each is independently selected from substituted or unsubstituted arylene or heteroarylene; the substituents for the arylene and heteroarylene groups are independently selected from arylene or heteroarylene;
Ar1、Ar2and Ar3Each independently selected from substituted or unsubstituted aryl or heteroaryl;
R1、R2and R3Each independently selected from H, substituted or unsubstituted aryl or heteroaryl.
Optionally, Z is1、Z2And Z3Are N, or Z1、Z2And Z3Are all N.
Optionally, L islAnd L2The same or different, and each is independently selected from any one of:
a. a substituted or unsubstituted monocyclic arylene;
b. a substituted or unsubstituted monocyclic heteroarylene group containing 1 to 3N atoms;
c. substituted or unsubstituted fused ring groups formed by fusing a and/or b;
the total number of a and/or b in the fused 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 fusing 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 pyrimidinyl group, a pyridazinylene group, a 1,2, 3-triazinylene group, a 1,3, 5-triazinylene group or a 1,3, 4-triazinylene group.
Optionally, L islAnd L2The same or different, and each is independently selected from the group consisting of substituted or unsubstituted phenylene, pyridylene, pyrazinylene, pyrimidinyl, pyridazinylene, 1,2, 3-triazinylene, 1,3, 5-triazinylene, 1,3, 4-triazinylene, naphthylene, anthrylene, phenanthrylene, quinolinylene, isoquinolinylene, quinoxalylene, 1, 5-naphthyridinylene, and 1, 6-naphthyridinylene;
the substituent of the above groups is selected from phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, carbazolyl, benzodifuran, benzodithiophene or fluorenyl.
Optionally, Ar is1、Ar2And Ar3Each 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 fused ring group formed by fusing a and/or b;
the total number of a and/or b in the fused 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 fusing 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 pyrimidinyl group, a pyridazinylene group, a 1,2, 3-triazinylene group, a 1,3, 5-triazinylene group or a 1,3, 4-triazinylene group.
Optionally, Ar is1、Ar2And Ar3Each independently selected from phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, naphthyl, anthracyl, phenanthryl, quinolinyl, isoquinolinyl, quinoxalinyl, 1, 5-naphthyridinyl or 1, 6-naphthyridinyl.
Optionally, the R is1、R2And R3Each independently selected from H or 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. substituted or unsubstituted fused ring groups formed by fusing a and/or b;
in the fused ring group, the total number of a and/or b is 2-3;
the substituents of a, b and c are independently selected from monocyclic aryl, monocyclic heteroaryl, fused ring groups formed by fusing 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 pyrimidinyl group, a pyridazinylene group, a 1,2, 3-triazinylene group, a 1,3, 5-triazinylene group or a 1,3, 4-triazinylene group.
Optionally, the R is1、R2And R3Each independently selected from H, phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, naphthyl, anthracenyl, phenanthrenyl, quinolinyl, isoquinolinyl, quinoxalinyl, 1, 5-naphthyridinyl or 1, 6-naphthyridinyl.
Optionally, the N-containing heterocyclic compound has any one of the following structures:
Figure BDA0003531678900000051
Figure BDA0003531678900000061
Figure BDA0003531678900000071
Figure BDA0003531678900000081
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 those 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 (a magnesium-silver electrode, the mass ratio of magnesium to silver is 1:9) and a cap layer (CPL).
In the invention, the anode material of the organic light-emitting device can be selected from metal-copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum and the like and alloys thereof; such as metal oxide-indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), etc.; such as conductive polymers-polyaniline, polypyrrole, poly (3-methylthiophene), and the like, and in addition to the above materials that facilitate hole injection and combinations thereof, include known materials suitable for use as anodes.
In the invention, 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 metal material-LiF/Al, LiO2/Al、BaF2Al, etc.; in addition to the above materials and combinations thereof that facilitate electron injection, known materials suitable for use as cathodes are also included.
In an alternative embodiment of the present invention, the organic optoelectronic device, for example, the organic thin film layer in the 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).
In an alternative embodiment of the present 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 a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or 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 device, wherein the organic light emitting display device may be a display screen of a mobile phone, a display screen of a computer, a display screen of a television, a display screen of a smart watch, a display panel of a smart car, a display screen of a VR or AR helmet, a display screen of various smart devices, and the like.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation of the substrate
Preparation of Sub1
Figure BDA0003531678900000101
A1L reaction vessel was charged with mid1-1(20g, 90.4mmol), 4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborane (27.8g, 180.8mmol), dioxane (400ml) and PdCl2(dtbpf) (5.92g, 9mmol), reacted for 0.5h under nitrogen, then K was injected3PO4The solution (0.576g/ml, 100ml) was heated to 80 ℃ and reacted overnight with TCL tracing until the starting 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 eluting with ethyl acetate/petroleum ether (10%, v/v) to give mid1-2(10g, 65%).
Into a reaction vessel, 250ml of dimethyl sulfoxide, 2-iodoxybenzoic acid (28g,100mmol) and I were charged2(25.4g,100mmol), dissolved by stirring at room temperature for 20min, then mid1-2(8.5g, 50mmol) and 10ml glacial acetic acid were added, followed by reaction at 70 ℃ for 30 min, followed by rapid temperature rise to 120 ℃ for 12 h, distillation under reduced pressure, removal of the solvent, and isolation by column chromatography gave mid1-3(4g, 44%).
200ml of ethanol, mid1-3(36.2g, 200mmol), NBS (5g, 440mmol) and copper nitrate (3.75g, 20mmol) were added successively to the reactor, and the mixture was stirred at room temperature for 0.5 hour, and then warmed to 50 ℃ for 3 hours. The TCL followed the reaction until the feed point disappeared. The temperature is reduced to 20 ℃, the reaction liquid is poured into 200ml of water, and the mixture is stirred for 2 hours. Suction filtration is carried out, the filter cake is stirred for 1 hour at the water temperature of 200ml, suction filtration and drying at 50 ℃ are carried out, thus obtaining mid1-4(37g, 55%).
A2L two-necked flask was charged with midd 1-4(50g,148mmol) and methylene chloride (1L), and then titanium tetrachloride (1M,232ml) and dimethylamine borane complex (21.5ml) were slowly added dropwise at 0 ℃ to react at 0 ℃ for 2 hours, followed by neutralization with sodium carbonate (1M). 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 t-butanol (34g,300mmol) was dissolved in dimethyl sulfoxide (250ml), and after stirring for 1 hour, methyl iodide (43g,300mmol) was added dropwise and the mixture was stirred at 80 ℃ for 12 hours. The organic layer was separated from acetone and water, dried over magnesium sulfate and then distilled under reduced pressure. Column on hexane silica afforded the product sub1(22g, 43%).
Preparation of Sub2
Figure BDA0003531678900000111
A1L reactor was charged with bromobenzene (36g,330mmol), dissolved in tetrahydrofuran (200L), and then butyllithium (2.5M, 154.4ml) was slowly added dropwise at-78 ℃ and stirred for 2 hours. Then, midl-4(50g,148mmol) dissolved in tetrahydrofuran (300ml) was slowly dropped into the reactor at-78 ℃ and stirred for 24 hours while maintaining the ordinary temperature. After the reaction is finished, the sodium carbonate 1M solution is neutralized. The organic layer was separated, the tetrahydrofuran was removed, extracted twice with ethyl acetate and distilled water and dried. The mixture was placed under a nitrogen atmosphere, and then benzene (11.1g, 45.2mmol) and 570mL of dichloromethane were added. Boron trifluoride diethyl etherate (5.7mL, 45.2mmol) dissolved in methylene chloride was slowly added dropwise to the system. Stirring at room temperature for 2 hours. The reaction was stopped with methanol and distilled water, the organic layer was extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and compound sub2(14.51g, 85%) was purified by column chromatography.
Preparation of Sub3
Figure BDA0003531678900000112
After 2-bromobiphenyl (54g, 232mmol) was dissolved in tetrahydrofuran (200L) in a 1L reaction vessel, butyllithium (2.5M, 154.4ml) was slowly added dropwise at a low temperature of-78 ℃ and then stirred for 2 hours. Thereafter, mid1-4(50g,148mmol) dissolved in tetrahydrofuran (300ml) was slowly dropped at-78 ℃ and stirred at room temperature for 24 hours. After the reaction was completed, the sodium carbonate solution was neutralized with 1M sodium carbonate. The organic layer was separated, the tetrahydrofuran removed by rotary evaporation, extracted twice with ethyl acetate and distilled water and dried. Then, hydrochloric acid (10ml) and acetic acid (350ml) were added thereto, followed by stirring under reflux for 24 hours. After the reaction solution was cooled at room temperature, the solid was filtered and washed with methanol several times. Isolation on a hexane silica gel column gave the product sub3(28g, 40%).
Preparation of Sub4
Figure BDA0003531678900000121
Substitution of mid1-3 for mid4-1 produced mid4-2 in the same molar ratio used for mid 1-4.
Mid4-2(48.6g, 150mmol), Cs were added to the reaction vessel2CO3(48.9g, 150mmol) and CuCl (1.19g, 12 mmol). To N-methylpyrrolidone (300mL) were added acetylacetone (115mL) and bromobenzene (31g, 120mmol), and the reaction mixture was heated at 130 ℃ for 18 hours under an argon atmosphere. The suspension was cooled to ambient temperature. Adding saturated NaHCO to the suspension3(aqueous solution) (1L). The mixture was filtered. With saturated NaHCO3(aqueous solution) (1L) the filtrate was washed. 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) gave the product sub4(42g, 70%).
Preparation of Sub5
Figure BDA0003531678900000122
The preparation method of Sub5 is essentially identical to Sub4, except that the bromobenzene used in the preparation of Sub4 is replaced by 2-bromodibenzofuran.
Preparation of Sub6
Figure BDA0003531678900000123
To the reactor was added mid6-1(55g, 249mmol) and triethyl orthoformate (500 mL). The resulting mixture was refluxed for 4-8 hours until TLC showed complete consumption of the starting material spot. 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) gave the product mid6-2(40g, 95%).
Substitution of mid1-3 for mid6-2, sub6 was prepared at the same molar ratio used for mid 1-4.
Preparation of Sub7
Figure BDA0003531678900000131
Mid7-1(35g, 97mmol) was dissolved in tetrahydrofuran (250ml) and then 2-bromo-6-iodopyridine (30g, 106mmol), palladium tetraphenylphosphine (4.3g, 3.72mmol), K were added2CO3(52g, 372mmol) and water, and stirred at 100 ℃ under reflux for 3 hours. When the reaction was completed, it was extracted with ethyl acetate and water, and the organic layer was extracted with anhydrous MgSO4Drying and concentration, separation and purification of the resulting organic material by means of a silica gel column gave mid7-2(33g, 88%).
In a reactor, mid7-2(10g, 25.8mmol) was dissolved in DMF (150ml) and then bis (pinacol) diboron (10g, 35.3mmol), Pd (dppf) Cl was added2(1.3g, 1.77mmol) and KOAc (23.5g, 170mmol) were stirred at 130 ℃ under reflux for 4 hours. When the reaction is complete, DMF is removed by distillation and taken up with CH2Cl2And water extraction. The organic layer was washed with MgSO4Drying and concentration, the resulting compound was subjected to silica gel column and recrystallization to give mid7-3(7g, 62%).
Replacing 2-bromo-6-iodopyridine for 1-bromo-4-iodobenzene produced mid7-4 in a manner consistent with that used to produce mid 7-2. Sub7 was then prepared in a manner consistent with the preparation of mid7-3, with mid7-2 being replaced with mid 7-4.
Preparation of Sub8
Figure BDA0003531678900000141
Substitution of mid7-1 for mid8-1, 2-bromo-6-iodopyridine for 1-bromo-4-iodonaphthalene to prepare mid8-2, followed by substitution of mid7-2 for mid8-2, sub8 was prepared in the same manner as for mid 7-3.
Preparation of Sub9
Figure BDA0003531678900000142
The preparation method of Sub9 is essentially identical to Sub4, except that the bromobenzene used in the preparation of Sub4 is replaced by 3-bromopyridine.
Preparation of Sub10
Figure BDA0003531678900000143
In accordance with the manner in which mid7-2 was prepared, mid10-2 was prepared by replacing 1-bromo-4-iodonaphthalene with mid10-1 and mid7-1 with 7- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) benzoxazole. Subsequently, mid7-2 was replaced with mid10-2, and mid10-3 was prepared in the same manner as mid 7-3. The corresponding reactants were also replaced to prepare mid10-4 and sub 10.
Preparation of E1
Figure BDA0003531678900000151
After completely dissolving the compound 2, 4-diphenyl-6- [4'- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine (10.0g, 19.6mmol) and sub1(7.0g, 19.9mmol) in 100ml of tetrahydrofuran under a nitrogen atmosphere, tetratriphenylphosphine palladium (620mg, 0.537mmol) was added thereto for half an hour, followed by potassium carbonate (7.4g, 53.7mmol) dissolved in 43ml of water, followed by heating and stirring for 7 hours. The reaction was completed by lowering the reaction temperature to room temperature, 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(9.5g, 74%).
Pinacol ester of phenylboronic acid (4.0g, 19.6mmol) and sub1-1(13.5g, 20.6mmol) were completely dissolved in 100ml of dimethyl sulfoxide under a nitrogen atmosphere, and tetratriphenylphosphine palladium (620mg, 0.537mmol) was added thereto for reaction for half an hour, followed by addition of potassium carbonate (7.4g, 53.7mmol), followed by heating and stirring for 30 hours. Then, the solvent was distilled off under reduced pressure, and the solid was washed with water several times, dried and purified by sublimation to obtain E1(9.5g, 74%).
Preparation of E2
Figure BDA0003531678900000161
The preparation method of E2 was identical to that of E1, and sub1 was replaced with sub2 in the same molar ratio according to the preparation method of E1.
Preparation of E3
Figure BDA0003531678900000162
The preparation of E3 was in accordance with E1, and sub1 was replaced with sub2, 2, 4-diphenyl-6- [4'- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine with 2, 4-diphenyl-6- [4'- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -3-yl ] -1,3, 5-triazine and sub1-1 with sub2-1 using the same molar ratios as in the preparation of E1.
Preparation of E4
Figure BDA0003531678900000171
The preparation process of E4 is identical to that of E1, and according to the preparation process of E1, sub1 is replaced with sub2, 2, 4-diphenyl-6- [4'- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine and sub1-1 is replaced with sub4-1, using the same molar ratio.
Preparation of E5
Figure BDA0003531678900000172
The preparation method of E5 was the same as that of E1, and sub1 was replaced with sub3 and sub1-1 was replaced with sub5-1 in the same molar ratio according to the preparation method of E1.
Preparation of E6
Figure BDA0003531678900000181
The preparation process of E6 is identical to that of E1, and according to the preparation process of E1, sub1 is replaced with sub2, 2, 4-diphenyl-6- [4'- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine and sub1-1 is replaced with sub6-1, using the same molar ratio.
Preparation of E7
Figure BDA0003531678900000182
The preparation method of E7 was the same as that of E1, and sub1 was replaced with sub4 and sub1-1 was replaced with sub7-1 in the same molar ratio according to the preparation method of E1.
Preparation of E8
Figure BDA0003531678900000191
The preparation method of E8 was the same as that of E1, and sub1 was replaced with sub5 and sub1-1 was replaced with sub8-1 in the same molar ratio according to the preparation method of E1.
Preparation of E9
Figure BDA0003531678900000192
The preparation method of E9 was the same as that of E1, and sub1 was replaced with sub4 and sub1-1 was replaced with sub9-1 in the same molar ratio according to the preparation method of E1.
Preparation of E10
Figure BDA0003531678900000201
The preparation method of E10 was the same as that of E1, and sub1 was replaced with sub6 and sub1-1 was replaced with sub10-1 in the same molar ratio according to the preparation method of E1.
Preparation of E11
Figure BDA0003531678900000202
The preparation process of E11 is identical to that of E1, and according to the preparation process of E1, sub1 is replaced with sub4, 2, 4-diphenyl-6- [4'- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) [1,1' -biphenyl ] -4-yl ] -1,3, 5-triazine and sub1-1 is replaced with sub11-1, using the same molar ratio.
The results of time-of-flight ("tof") analysis and elemental analysis of the compounds in the above examples by matrix-assisted laser desorption ionization are shown in table 1 below.
TABLE 1
Figure BDA0003531678900000203
Figure BDA0003531678900000211
Comparative example
Indium Tin Oxide (ITO) and a process for producing the same
Figure BDA0003531678900000212
The glass substrate coated with a thin film of (3) is put in distilled water in which a detergent is dissolved, and washed by ultrasonic waves. After washing ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes. After the completion of the distilled water washing, the resultant was ultrasonically washed with a solvent of isopropyl alcohol, acetone, or methanol, dried, and then transported to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transported to a vacuum evaporator.
The ITO prepared above is transparentOn the electrode, the following compound [ HI ] was added]To be provided with
Figure BDA0003531678900000222
The hole injection layer is formed by thermal vacuum deposition. Sequentially vacuum-depositing hexanitrile Hexaazatriphenylene (HAT) of the following chemical formula on the hole injection layer
Figure BDA0003531678900000224
And the following compound [ HT]
Figure BDA0003531678900000223
Thereby forming a hole transport layer.
Next, on the hole transport layer, the following compound [ BH]And [ BD ]]At a weight ratio of 25:1, in film thickness
Figure BDA0003531678900000228
Vacuum evaporation is performed to form a light emitting layer.
On the light-emitting layer, the following compound [ ET ]]And [ LiQ ]](8-hydroxyquinoline lithium, lithium) was vacuum-evaporated at a weight ratio of 1:1 to obtain a film
Figure BDA0003531678900000227
The thickness of (a) forms an electron injection and transport layer. On the above electron injection and transport layer, lithium fluoride (LiF) is sequentially added to
Figure BDA0003531678900000225
Thickness of aluminum and
Figure BDA0003531678900000226
the cathode is formed by vapor deposition to a certain thickness.
In the above process, the evaporation rate of the organic material is maintained at 0.4-0.4
Figure BDA00035316789000002211
Lithium fluoride maintenance of cathode
Figure BDA0003531678900000229
Deposition rate of (3), aluminum maintenance
Figure BDA00035316789000002210
The vapor deposition rate of (2), the degree of vacuum of which is maintained at 1X 10 during vapor deposition-7To 5X 10-8And supporting to thereby fabricate an organic light emitting device.
Figure BDA0003531678900000221
Figure BDA0003531678900000231
Experimental examples 1 to 11
An organic light-emitting device was produced in the same manner as in comparative example except that the compound synthesized in example 1 was used instead of the compound [ ET ] in the above comparative example.
The organic light-emitting devices manufactured in the above experimental examples and comparative examples using the respective compounds as electron transport layers were controlled at 10mA/cm2The driving voltage and the luminous efficiency were measured at a current density of 20mA/cm2The time required for the initial luminance to reach 95% was measured at the current density of (LT 95). The results are shown in table 2 below.
TABLE 2
Name (R) 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, compared with comparative examples, the organic light emitting device prepared from the compound provided by the present invention shows excellent device characteristics, and it can be concluded that the compound provided by the present invention can adjust the electron transport rate, further adjust the carrier balance of the device, and show a significant improvement in device performance (including light emitting efficiency and lifetime).
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (11)

1. An N-containing heterocyclic compound having the structure of formula i:
Figure FDA0003531678890000011
wherein X is selected from O, S, NR1Or CR2R3；
Z1、Z2And Z3Independently selected from N or C, and containing at least one N;
Lland L2The same or different, and each is independently selected from substituted or unsubstituted arylene or heteroarylene; the substituents for the arylene and heteroarylene groups are independently selected from arylene or heteroarylene;
Ar1、Ar2and Ar3Each independently selected from substituted or unsubstituted aryl or heteroaryl;
R1、R2and R3Each independently selected from H, substituted or unsubstituted aryl or heteroaryl.
2. The N-containing heterocyclic compound according to claim 1, characterized in that Z is1、Z2And Z3Are N, or Z1、Z2And Z3Are all N.
3. The N-containing heterocyclic compound according to claim 1, characterized in that L islAnd L2The same or different, and each is independently selected from any one of:
a. a substituted or unsubstituted monocyclic arylene;
b. a substituted or unsubstituted monocyclic heteroarylene group containing 1 to 3N atoms;
c. substituted or unsubstituted fused ring groups formed by fusing a and/or b;
the total number of a and/or b in the fused 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 fusing monocyclic aryl and/or monocyclic heteroaryl.
4. The N-containing heterocyclic compound according to claim 3, characterized in that L islAnd L2The same or different, and each is independently selected from the group consisting of substituted or unsubstituted phenylene, pyridylene, pyrazinylene, pyrimidinyl, pyridazinylene, 1,2, 3-triazinylene, 1,3, 5-triazinylene, 1,3, 4-triazinylene, naphthylene, anthrylene, phenanthrylene, quinolinylene, isoquinolinylene, quinoxalylene, 1, 5-naphthyridinylene, and 1, 6-naphthyridinylene;
the substituent of the above groups is selected from phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, carbazolyl, benzodifuran, benzodithiophene or fluorenyl.
5. The N-containing heterocyclic compound according to claim 1, characterized in that Ar is1、Ar2And Ar3Each 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. substituted or unsubstituted fused ring groups formed by fusing a and/or b;
the total number of a and/or b in the fused 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 fusing monocyclic aryl and/or monocyclic heteroaryl.
6. The N-containing heterocyclic compound according to claim 5, characterized in that Ar is1、Ar2And Ar3Each independently selected from phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, naphthyl, anthracyl, phenanthryl, quinolinyl, isoquinolinyl, quinoxalinyl, 1, 5-naphthyridinyl or 1, 6-naphthyridinyl.
7. The N-containing heterocyclic compound according to claim 1, characterized in that R1、R2And R3Each independently selected from H or 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. substituted or unsubstituted fused ring groups formed by fusing a and/or b;
the total number of a and/or b in the fused 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 fusing monocyclic aryl and/or monocyclic heteroaryl.
8. The N-containing heterocyclic compound according to claim 7, characterized in that R is1、R2And R3Each independently selected from H, phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, 1,2, 3-triazinyl, 1,3, 5-triazinyl, 1,3, 4-triazinyl, naphthyl, anthracenyl, phenanthrenyl, quinolinyl, isoquinolinyl, quinoxalinyl, 1, 5-naphthyridinyl or 1, 6-naphthyridinyl.
9. The N-containing heterocyclic compound according to claim 1, characterized by having any one of the following structures:
Figure FDA0003531678890000031
Figure FDA0003531678890000041
Figure FDA0003531678890000051
Figure FDA0003531678890000061
10. 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 transporting layer containing at least one N-containing heterocyclic compound according to any one of claims 1 to 9.
11. A display device comprising the display panel of claim 10.
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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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