CN112687797A - Organic electroluminescent device and display device comprising same - Google Patents

Organic electroluminescent device and display device comprising same Download PDF

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CN112687797A
CN112687797A CN202110034259.8A CN202110034259A CN112687797A CN 112687797 A CN112687797 A CN 112687797A CN 202110034259 A CN202110034259 A CN 202110034259A CN 112687797 A CN112687797 A CN 112687797A
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organic electroluminescent
electroluminescent device
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CN112687797B (en
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陈跃
丰佩川
邢其锋
邱创弘
陈义丽
孙伟
王鹏程
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Yantai Xianhua Photoelectric Material Research Institute Co ltd
Yantai Haisen Big Data Co ltd
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Abstract

The application provides an organic electroluminescent device, which comprises a substrate, an anode electrode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a cathode electrode and a light extraction layer, wherein the light extraction layer comprises a compound shown in a general formula (I). The light extraction layer has high refractive index, and the luminous efficiency of the organic electroluminescent device can be improved. The present application also provides a display device comprising the organic electroluminescent device of the present application.
Figure DDA0002893542320000011

Description

Organic electroluminescent device and display device comprising same
Technical Field
The present disclosure relates to the field of organic light emitting display technologies, and in particular, to an organic electroluminescent device and a display apparatus including the same.
Background
An organic electroluminescent device is a multi-layered organic thin film structure in which a light emitting layer is positioned between a cathode and an anode. Light emitted from the light-emitting layer after energization is transmitted from the transparent electrode side, and the light is lost due to a waveguide effect such as total reflection between the respective film layers. A light extraction layer with high refractive index is added on the transparent electrode, so that the light extraction efficiency can be greatly improved.
The light extraction layer may be an inorganic compound or an organic compound. The inorganic compound has the characteristics of high refractive index and favorable light extraction, but the coating temperature is very high (>1000 ℃), and the coating can damage organic components. The organic film has low vapor deposition temperature and has more advantages than inorganic compounds in process. Organic electroluminescent diode (OLED) elements basically use organic light extraction materials that can improve the light extraction efficiency of OLEDs. The refractive index is the most important index of the light extraction material, and generally, the higher the refractive index of the light extraction layer is, the higher the light extraction efficiency from the electrode to the light extraction layer is, and the higher the light emission efficiency of the OLED is.
The material currently used mainly for the OLED light extraction layer is an aromatic amine compound of japanese bentonite valley (CN 103828485A).
The refractive index of such compounds (e.g., compounds 1-1 and 1-2) remains to be improved.
Figure BDA0002893542300000011
Figure BDA0002893542300000012
Disclosure of Invention
In view of the above problems of the prior art, it is an object of the present application to provide an organic electroluminescent device having high luminous efficiency. A first aspect of the present application provides an organic electroluminescent device comprising:
a substrate, an anode electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode electrode and a light extraction layer;
the light extraction layer includes a compound of formula (I):
Figure BDA0002893542300000021
wherein Ar is1And Ar2Each independently selected from H atom, deuterium atom, halogen, C6-C30Aryl or C of3-C30Each independently hydrogen atom on said aryl and heteroaryl groups may be substituted with Ra, each independently heteroatom on said heteroaryl group is selected from O, S and N, each independently Ra is selected from deuterium, halogen, C1-C6Alkyl, phenyl, biphenyl, terphenyl, or naphthyl;
L1、L2and L3Each independently selected from phenylene or phenyleneA pyridyl group.
In a second aspect, the present application provides a display device comprising an organic electroluminescent device as provided herein.
The application provides an organic electroluminescent device, including the light extraction layer of high refracting index, utilize the advantage that light extraction layer refracting index is high, promote light to take out more effectively to organic electroluminescent device's luminous efficacy has been promoted. The display device provided by the application has an excellent display effect.
Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only one embodiment of the present application, and other embodiments can be obtained by those skilled in the art according to the drawings.
Fig. 1 is a schematic view of an organic electroluminescent device according to an embodiment of the present application.
Detailed Description
The technical solutions in the present application will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in this application are within the scope of protection of this application.
A first aspect of the present application provides an organic electroluminescent device comprising:
a substrate, an anode electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode electrode and a light extraction layer;
the light extraction layer includes a compound of formula (I):
Figure BDA0002893542300000031
wherein Ar is1And Ar2Each independently selected from H atom, deuterium atom, halogen, C6-C30Aryl or C of3-C30Each independently hydrogen atom on said aryl and heteroaryl groups may be substituted with Ra, each independently heteroatom on said heteroaryl group is selected from O, S and N, each independently Ra is selected from deuterium, halogen, C1-C6Alkyl, phenyl, biphenyl, terphenyl, or naphthyl;
L1、L2and L3Each independently selected from phenylene or pyridylene.
Preferably, said L1、L2And L3Each independently selected from the group consisting of:
Figure BDA0002893542300000032
the attachment sites are indicated in the figure.
Preferably, Ar is1And Ar2Each independently selected from the group consisting of:
Figure BDA0002893542300000041
wherein the content of the first and second substances,
R1and R2Each independently selected from C1-C6Alkyl of (C)6-C12Aryl or C of3-C12The heteroaryl group of (a).
For example, the compound of formula (I) may be selected from the following compounds:
Figure BDA0002893542300000051
Figure BDA0002893542300000061
preferably, the hole transport layer comprises a compound of formula (II):
Figure BDA0002893542300000062
wherein the content of the first and second substances,
Ar3and Ar4Each independently selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rb;
R3-R6each independently selected from hydrogen, deuterium, C1-C10Alkyl of (C)3-C6Cycloalkyl of, C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rb, said R3-R6Wherein two adjacent groups can be connected to form a ring;
R7and R8Each independently selected from C1-C10Alkyl of (C)3-C6Cycloalkyl of, C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rb, said R7And R8Can be connected into a ring;
x is selected from O, S, CR9R10、NR11，R9And R10Each independently selected from C1-C10Alkyl of (C)3-C6Cycloalkyl of, C6-C30Aryl or C of3-C30The heteroaryl of (A), the R11Is selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rb, said R9And R10Can be connected into a ring;
l is selected from the group consisting of a bond、C6-C30Arylene group of (A) or (C)3-C30The heteroarylene of (a), wherein the hydrogen atoms on the arylene and heteroarylene, independently of each other, may be substituted with Rb;
each heteroatom on the heteroaryl or heteroarylene is independently selected from O, S, N;
each Rb is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
For example, the compound of formula (II) may be selected from the following compounds:
Figure BDA0002893542300000071
Figure BDA0002893542300000081
preferably, the electron transport layer comprises a compound of formula (III):
Figure BDA0002893542300000082
wherein the content of the first and second substances,
R12-R17each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rc, and R12-R14Wherein two adjacent groups can be linked to form a ring, and R16And R17Can be connected into a ring;
a is selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc;
y is selected from O, S, CR18R19，R18And R19Each independentlyIs selected from C1-C6Alkyl of (C)5-C20Cycloalkyl of, C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rc, and R18And R19Can be connected into a ring;
X1-X4each independently selected from CR20Or N, R20Selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rc, and adjacent R20Can be connected into a ring;
L1and L2Each independently selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Rc;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from O, S, N;
each Rc is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
For example, the compound of formula (III) may be selected from the following compounds:
Figure BDA0002893542300000091
Figure BDA0002893542300000101
in the present application, there is no particular limitation on the kind and structure of the organic electroluminescent device, and it may be an organic electroluminescent device of various types and structures known in the art.
The organic electroluminescent device of the present application may be a light-emitting device having a top emission structure, and may have a structure including an anode electrode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a transparent or translucent cathode, and a light extraction layer in this order on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a bottom emission structure, and may include a light extraction layer, a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode electrode, which are sequentially included on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a double-sided light-emitting structure, and may include a light extraction layer, a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a transparent or translucent cathode, and a light extraction layer, which are sequentially included on a substrate.
In some embodiments of the present application, an electron blocking layer may be further disposed between the hole transport layer and the light emitting layer, and a hole blocking layer may be disposed between the light emitting layer and the electron transport layer.
Fig. 1 shows a schematic view of an organic electroluminescent device according to an embodiment of the present application, in which a substrate 1, an anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, a cathode electrode 8, and a light extraction layer 9 are sequentially disposed from bottom to top.
It is to be understood that fig. 1 schematically illustrates the structure of a typical organic electroluminescent device, and the present application is not limited to this structure.
For convenience, the organic electroluminescent device of the present application is described below with reference to fig. 1, but this is not meant to limit the scope of the present application in any way.
In the present application, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, for example, glass, polymer materials, glass with TFT elements, polymer materials, and the like may be used.
In the present application, the anode electrode 2 is not particularly limited and may be selected from anode electrodes known in the art. For example, metals, alloys or conductive compounds have a high work function (4eV or more than 4 eV). The metal may be Au, Ag, etc. The conductive transparent material can be selected from CuI, Indium Tin Oxide (ITO), SnO2And ZnO, or an amorphous material such as IDIXO (In) which can form a transparent conductive film2O3-ZnO). The thickness of the anode is in the range of 10 to 1,000 nm. Wherein the thickness of the anode electrode varies depending on the material used.
In the present application, the material of the hole injection layer 3 is not particularly limited, and may be made of a hole injection layer material known in the art, for example, a Hole Transport Material (HTM) is selected as the hole injection material.
In a preferred embodiment, the hole injection layer 3 may further include a p-type dopant, the type of which is not particularly limited, and various p-type dopants known in the art may be used, for example, the following p-type dopants may be used:
Figure BDA0002893542300000111
in the present application, the amount of the p-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the hole transport layer 4 is not limited at all, and a hole transport material known to those skilled in the art may be used. In a preferred embodiment, the hole transport layer 4 may comprise at least one of the hole transport materials of the present application, or a combination of at least one of the hole transport materials of the present application with at least one of the following known hole transport materials HT-1 to HT-32.
For example, the material for the hole injection layer host and the material for the hole transport layer may be selected from at least one of the following HT-1 to HT-32 compounds:
Figure BDA0002893542300000121
Figure BDA0002893542300000131
in the present application, the light emitting layer 5 may include a blue light emitting layer, a green light emitting layer, or a red light emitting layer, the light emitting material in the light emitting layer 5 is not particularly limited, and various light emitting materials known to those skilled in the art may be used, for example, the light emitting material may include a host material and a light emitting dye.
In a preferred embodiment, the blue-light host material may be selected from at least one of the following BH-1 to BH-36 compounds:
Figure BDA0002893542300000132
Figure BDA0002893542300000141
Figure BDA0002893542300000151
in a preferred embodiment, the green host material may be selected from at least one of the following GPH-1 to GPH-82 compounds:
Figure BDA0002893542300000152
Figure BDA0002893542300000161
Figure BDA0002893542300000171
Figure BDA0002893542300000181
in a preferred embodiment, the red host material may be selected from at least one of the following RH-1 to RH-10 compounds:
Figure BDA0002893542300000182
Figure BDA0002893542300000191
in a preferred embodiment of the present application, the light-emitting layer 5 employs the technique of electroluminescence. The luminescent dye in the luminescent layer 5 thereof is a fluorescent or phosphorescent dopant, which may be selected from, but not limited to, at least one of the following blue dyes BD01 to BD04 compounds, at least one of the green dyes GD01 to GD04 compounds, or at least one of the red dyes RPD-1 to RPD-28 compounds. The amount of the dopant is not particularly limited and may be an amount well known to those skilled in the art.
Figure BDA0002893542300000192
Figure BDA0002893542300000201
In the present application, the electron transport layer 6 is not particularly limited, and an electron transport material known to those skilled in the art may be used. In a preferred embodiment, the electron transport layer 6 comprises at least one of the electron transport materials herein, and in another preferred embodiment, the electron transport layer 6 may also comprise a combination of at least one of the electron transport materials herein and at least one of the following known electron transport materials ET-1 to ET-58:
Figure BDA0002893542300000211
Figure BDA0002893542300000221
Figure BDA0002893542300000231
in a preferred embodiment, the electron transport layer 6 may further include an n-type dopant, the kind of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be used, for example, the following n-type dopants may be used:
Figure BDA0002893542300000241
in the present application, the amount of the n-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and for example, may include, but are not limited to, LiQ, LiF, NaCl, CsF, Li in the prior art2O、Cs2CO3At least one of BaO, Na, Li, Ca and the like.
In the present application, the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, a magnesium silver mixture, LiF/Al, ITO, Al, and other metals, metal mixtures, oxides, and other materials.
In the present application, the light extraction layer 9 comprises at least one of the light extraction layers of the present application, and the light extraction layer 9 may also comprise a combination of at least one of the light extraction layers of the present application and a known light extraction layer. The light extraction layer known so far is mainly a light extraction layer containing an aromatic amine compound. In order to improve the light extraction efficiency, the light extraction layer of the present application is provided on the transparent electrode on the light extraction side. The refractive index of the light extraction layer is required to be larger than that of the electrode and to transmit visible light. The light extraction layer of the present application has a high refractive index and thus can provide a high light extraction rate. Preferably, the refractive index of the light extraction layer of the present application is > 1.85.
In some embodiments of the present application, the light extraction layer has a refractive index of red light of 1.85 or more, a refractive index of green light of 1.90 or more, and a refractive index of blue light of 2.00 or more.
In some embodiments of the present application, the thickness of the light extraction layer is 50 to 90nm, preferably 60 to 80 nm.
The present application also provides a display device comprising the organic electroluminescent device of the present application. The display device includes, but is not limited to, a display, a television, a mobile communication terminal, a tablet computer, and the like.
The method for preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be used, for example, the present application may be prepared by the following preparation method:
(1) cleaning an anode electrode 2 on an OLED device substrate 1 for top emission, respectively carrying out steps of medicinal washing, water washing, hairbrush, high-pressure water washing, air knife and the like in a cleaning machine, and then carrying out heat treatment;
(2) vacuum evaporating a hole injection layer 3 on the reflecting anode electrode 2, wherein the hole injection layer 3 contains a main body material and a p-type dopant;
(3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;
(4) a luminescent layer 5 is evaporated on the hole transport layer 4 in vacuum, and the luminescent layer 5 contains a host material and a luminescent dye;
(5) vacuum evaporating an electron transport material on the light emitting layer 5 to form an electron transport layer 6, wherein the electron transport layer 6 contains a host material and an n-type dopant;
(6) vacuum evaporating electron injection material selected from LiQ, LiF, NaCl, CsF, and Li on the electron transport layer 6 as electron injection layer 72O、Cs2CO3、BaOAt least one of Na, Li, Ca and the like;
(7) vacuum evaporating cathode material on the electron injection layer 7 as a cathode electrode 8;
(8) finally, a light extraction material is vapor-deposited on the cathode electrode 8 as a light extraction layer 9.
The above description has been made only of the structure of a typical organic electroluminescent device and a method for manufacturing the same, and it should be understood that the present application is not limited to this structure.
Synthesis example 1: synthesis of Compound LEM-1
Figure BDA0002893542300000251
Into a reaction flask were charged 100mmol of 2-bromo-triphenylene, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1 mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4). The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-triphenylene.
100mmol of M1, 100mmol of 4- (biphenyl) -4-benzidine, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of palladium (dibenzylideneacetone) (Pd (dba)) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. And stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder LEM-1. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ9.55(s,1H),9.25(s,1H),8.51–8.28(m,3H),7.75-7.68(m,7H),7.64(s,2H),7.57–7.46(m,11H),7.39(d,J＝10.0Hz,7H).
M/Z: experimental value, 623.1; theoretical value, 623.2.
Synthesis example 2: synthesis of Compound LEM-3
Figure BDA0002893542300000261
Into a reaction flask were charged 100mmol of 2-bromo-triphenylene, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-triphenylene.
100mmol of M1, 100mmol of 4- (2-naphthylbiphenyl) -4- (2-naphthyl) aniline, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction vessel. The reaction was carried out at 120 ℃ for 12 h. And stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder LEM-3. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ9.48(s,1H),8.92(s,1H),8.35(d,J＝10.0Hz,2H),8.30(s,2H),8.11(dd,J＝12.0,8.0Hz,7H),7.70(s,1H),7.63(d,J＝8.0Hz,6H),7.60–7.40(m,12H),7.38(d,J＝8.4Hz,6H).
M/Z: experimental value, 723.1; theoretical value, 723.3.
Synthetic example 3: synthesis of Compound LEM-10
Figure BDA0002893542300000271
Into a reaction flask were charged 100mmol of 2-bromo-triphenylene, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, and adding waterThe organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to give white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-triphenylene.
100mmol of M1, 100mmol of aniline, 28.8g of sodium tert-butoxide (300mmol), 800ml of toluene and 1 mol% of Pd (dba) are added to the reaction vessel. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
Into a reaction flask were charged 100mmol of 2-chlorobenzoxazole, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the 2-chlorobenzoxazole.
100mmol of M2, 100mmol of M3, 28.8g of sodium tert-butoxide (300mmol), 800ml of toluene and 1 mol% of Pd (dba) are added to the reaction vessel. The reaction was carried out at 120 ℃ for 12 h. And stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder LEM-10. Wherein Pd (dba) is added in an amount of 1 mol% based on M2.
1H NMR(400MHz,Chloroform)δ9.50(s,1H),9.24(s,1H),8.50–8.37(m,3H),7.76–7.68(m,6H),7.64(s,2H),7.54(d,J＝12.0Hz,5H),7.38(d,J＝8.4Hz,6H),7.24(s,2H),7.08(s,2H),7.00(s,1H).
M/Z: experimental value, 588.3; theoretical value, 588.2.
Synthetic example 4: synthesis of Compound LEM-15
Figure BDA0002893542300000281
Into a reaction flask were charged 100mmol of 2-bromo-triphenylene, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-triphenylene.
100mmol of M1, 100mmol of 4-benzidine, 28.8g of sodium tert-butoxide (300mmol), 800ml of toluene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
Into a reaction flask were charged 100mmol of 2-bromo (9, 9-dimethylfluorene), 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein, Pd (PPh)3)4Is 1 mol% of 2-bromo (9, 9-dimethylfluorene).
100mmol of M2, 100mmol of M3, 28.8g of sodium tert-butoxide (300mmol), 800ml of toluene and 1 mol% of Pd (dba) are added to the reaction vessel. The reaction was carried out at 120 ℃ for 12 h. And stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder LEM-10. Wherein Pd (dba) is added in an amount of 1 mol% based on M2.
1H NMR(400MHz,Chloroform)δ9.60(s,1H),9.26(s,1H),8.51–8.17(m,3H),8.09(s,1H),8.02(s,1H),7.90(s,1H),7.77(d,J＝12.0Hz,4H),7.85–7.67(m,5H),7.63(ddd,J＝14.4,10.0,8.0Hz,12H),7.41(s,1H),7.36(d,J＝13.6Hz,6H),7.24(s,1H),1.69(s,6H).
M/Z: experimental value, 739.4; theoretical value, 739.3.
Synthesis example 5: synthesis of Compound LEM-18
Figure BDA0002893542300000291
Into a reaction flask were charged 100mmol of triphenylene-2-pinacol ester, 100mmol of 2-bromo-5-chloropyridine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (B) added was 1 mol% based on the amount of 2-bromo-5-chloropyridine.
100mmol of M1, 100mmol of 4- (2-naphthylbiphenyl) -4- (2-naphthyl) aniline, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction vessel. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder LEM-18. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ9.60(s,1H),9.18(s,1H),8.54(s,1H),8.32(d,J＝12.0Hz,2H),8.08(d,J＝12.0Hz,3H),7.91(d,J＝10.0Hz,5H),7.70(s,1H),7.63(t,J＝8.0Hz,6H),7.60–7.39(m,10H),7.38(d,J＝8.0Hz,6H),6.82(s,1H).
M/Z: experimental value, 724.4; theoretical value, 724.3.
Synthetic example 6: synthesis of Compound LEM-19
Figure BDA0002893542300000301
Into a reaction flask were charged 100mmol of triphenylene-2-pinacol ester, 100mmol of 2-bromo-5-chloropyridine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (B) added was 1 mol% based on the amount of 2-bromo-5-chloropyridine.
100mmol of M1, 100mmol of 4- (2-naphthyl) aniline, 28.8g of sodium tert-butoxide (300mmol), 800ml of toluene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
Into a reaction flask were charged 100mmol of 2-naphthylboronic acid, 100mmol of 2-bromo-5-chloropyridine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein, Pd (PPh)3)4The amount of (B) added was 1 mol% based on the amount of 2-bromo-5-chloropyridine.
100mmol of M2, 100mmol of M3, 28.8g of sodium tert-butoxide (300mmol), 800ml of toluene and 1 mol% of Pd (dba) are added to the reaction vessel. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder LEM-19. Wherein Pd (dba) is added in an amount of 1 mol% based on M2.
1H NMR(400MHz,Chloroform)δ9.60(s,1H),9.17(s,1H),8.85(s,1H),8.55(t,J＝6.4Hz,1H),8.45(d,J＝12.0Hz,3H),8.32(d,J＝10.0Hz,4H),8.08(d,J＝12.0Hz,4H),7.94(t,J＝10.0Hz,4H),7.70(d,J＝8.8Hz,1H),7.60–7.40(m,12H),7.38(d,J＝8.0Hz,2H),6.82(s,1H).
M/Z: experimental value, 725.1; theoretical value, 725.3.
Synthetic example 7: synthesis of Compound LEM-24
Figure BDA0002893542300000311
Into a reaction flask were charged 100mmol of 2-bromo-triphenylene, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-triphenylene.
Into a reaction flask were charged 200mmol of M1, 100mmol of 4-benzidine, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene, and 1 mol% Pd (dba) was added. The reaction was carried out at 120 ℃ for 12 h. And stopping the reaction after the reaction is finished, cooling the reaction product to room temperature, adding water, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder LEM-24. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ9.60(s,1H),8.50–8.26(m,3H),7.94(s,2H),7.88–7.66(m,12H),7.57–7.46(m,6H),7.38–7.16(m,12H),7.09(d,J＝10.0Hz,3H).
M/Z: experimental value, 773.2; theoretical value, 773.3.
Synthesis example 8: synthesis of Compound LEM-27
Figure BDA0002893542300000312
Into a reaction flask were charged 100mmol of 2-bromo-triphenylene, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-triphenylene.
100mmol of M1, 100mmol of 4-benzidine, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of bromopentafluorobenzene, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene, and 1 mol% of Pd (dba) were added. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder LEM-27. Wherein Pd (dba) is added in an amount of 1 mol% based on M2.
1H NMR(400MHz,Chloroform)δ9.60(s,1H),9.23(s,1H),8.50–8.17(m,6H),7.75-7.64(m,4H),7.57–7.46(m,6H),7.39(d,J＝10.0Hz,6H).
M/Z: experimental value, 637.1; theoretical value, 637.2.
Synthetic example 9: synthesis of Compound LEM-28
Figure BDA0002893542300000321
Into a reaction flask were charged 100mmol of 2-bromo-triphenylene, 100mmol of 4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-triphenylene.
100mmol of M1, 100mmol of 4-amino-p-terphenyl, 28.8g of sodium tert-butoxide (300mmol), 1000ml of xylene and 1 mol% of Pd (dba) were added to the reaction flask. The reaction was carried out at 120 ℃ for 18 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of pentadeuterated bromobenzene, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene, and 1 mol% of Pd (dba) were added. The reaction was carried out at 120 ℃ for 18 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder LEM-28. Wherein Pd (dba) is added in an amount of 1 mol% based on M2.
1H NMR(400 MHz,Chloroform)δ9.60(s,1H),9.23(s,1H),8.50-8.27(m,3H),7.75-7.56(m,6H),7.52–7.44(m,3H),7.37-7.28(d,8H).
M/Z: experimental value, 631.1; theoretical value, 631.3.
Example 1
Arranging a reflective anode electrode on a glass substrate, wherein the anode electrode is an ITO (indium tin oxide) electrode, and the thickness of the electrode is 130 nm;
then, a hole injection layer with the thickness of 10nm is vacuum evaporated on the anode electrode, the material of the hole injection layer is HT-11 and p-type dopant p-1 with the mass ratio of 3%, wherein the evaporation rate is 0.1nm/s, and the selected material of the hole injection layer and the selected p-type dopant are respectively the following materials:
Figure BDA0002893542300000331
then, a 112nm hole transport layer is vacuum evaporated on the hole injection layer, wherein the material of the hole transport layer is HT-32, and the evaporation rate is 0.1 nm/s;
then, a luminescent layer is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a main material BH-1 and a luminescent dye BD-1, evaporation is carried out by using a multi-source co-evaporation method, wherein the evaporation rate of the main material BH-1 is adjusted to be 0.1nm/s, the evaporation rate of the dye BD-1 is 3% of the evaporation rate of the main material, the total evaporation film thickness is 20nm, and the main material and the luminescent dye are respectively the following materials:
Figure BDA0002893542300000341
then, an electron transport layer with the thickness of 35nm is vacuum-evaporated on the light emitting layer, the electron transport layer comprises an electron transport material ET-58 and an n-type dopant n-1, wherein the content of the n-type dopant is 50 mol%, and the electron transport material and the n-type dopant are respectively as follows:
Figure BDA0002893542300000342
then, an electron injection layer with the thickness of 40nm is vacuum evaporated on the electron transport layer, the material of the electron injection layer is Liq (8-hydroxyquinoline-lithium), and the evaporation speed is 0.1 nm/s;
then, a cathode electrode with the thickness of 18nm is evaporated on the electron injection layer in vacuum, the cathode electrode is made of a cathode material with the molar ratio of Mg to Ag being 1:9, and the evaporation rate is 1 nm/s;
and finally, vacuum evaporating a light extraction layer with the thickness of 50nm on the cathode electrode, wherein the material of the light extraction layer is LEM-1.
The organic electroluminescent device of the present embodiment emits blue light.
Examples 2 to 5
The same as example 1 except that the thickness of the light extraction layer was changed as shown in table 1.
Example 6
The examples were conducted in the same manner as example 1 except that the light-emitting host material and the light-emitting dye were replaced with GPH-82 and GD01, respectively.
Figure BDA0002893542300000351
The organic electroluminescent device of the present embodiment emits green light.
Examples 7 to 10
The same as example 6 was conducted except that the thickness of the light extraction layer was changed as shown in Table 1.
Example 11
The procedure of example 1 was repeated, except that the luminescent host material and the luminescent dye were replaced with RH-10 and RPD-1, respectively.
Figure BDA0002893542300000352
The organic electroluminescent device of the present embodiment emits red light.
Examples 12 to 15
The same as example 11 except that the thickness of the light extraction layer was changed as shown in table 1.
Examples 16 to 39
The same procedure as in the previous examples, except that LEM-3, LEM-10, LEM-15, LEM-18, LEM-19, LEM-24, LEM-27, LEM-28 were used instead of LEM-1, respectively, was repeated except that the thickness of the extraction layer was 70nm, as shown in Table 1.
Examples 40 to 42
The examples were the same as example 3 except that the hole transport materials were replaced with B6, B9, and B23, respectively, as shown in table 1.
Figure BDA0002893542300000361
Examples 43 to 45
The examples were the same as example 3 except that the electron transporting materials were replaced with C12, C27, and C28, respectively, as shown in table 1.
Figure BDA0002893542300000362
Example 46
The process was performed in the same manner as in example 31, except that the hole-transporting material was replaced with B6 and the electron-transporting material was replaced with C27 as shown in table 1.
The data and test results for examples 1-46 are detailed in tables 1 and 2.
Comparative example 1
The procedure was as in example 1 except that LEM-1 was replaced with Compound 1-1.
Figure BDA0002893542300000363
Comparative examples 2 to 5
The same as in comparative example 1 except that the thickness of the light extraction layer was changed as shown in table 1.
Comparative example 6
The procedure was as in example 6 except that LEM-1 was replaced with Compound 1-1.
Comparative examples 7 to 10
The same as in comparative example 6 except that the thickness of the light extraction layer was changed as shown in table 1.
Comparative example 11
The procedure was as in example 11 except that LEM-1 was replaced with Compound 1-1.
Comparative examples 12 to 15
The same as in comparative example 11 except that the thickness of the light extraction layer was changed as shown in Table 1.
Comparative examples 16 to 18
The same as in the above comparative example, in which the thickness of the extraction layer was 70nm, was followed except that the compound 1-1 was replaced with the compound 1-2.
Figure BDA0002893542300000371
The data and test results for comparative examples 1-18 are detailed in tables 1 and 2.
Measurement of refractive index
The measuring instrument is a Version-1.0.1.4 spectrum ellipsometer of a Radiation technology company; the size of the glass substrate is 200mm multiplied by 200mm, and the thickness of the material film is 80 nm. The refractive index of the compound at different wavelengths was measured.
Performance detection of organic electroluminescent device
Specifically, the BJV test system was used to test the current efficiency and CIE color coordinates of the organic electroluminescent device.
For a blue light device, blue light index (BI) is used for inspecting the luminous efficiency of the blue light device, the CIEy value is mainly used for evaluating the saturation of the blue light color, the blue light index is obtained by dividing the current efficiency of the blue light device by the CIEy value, the increase of the CIEy value indicates that the blue light color generates red shift, and the decrease of the CIEy value indicates that the blue light color generates blue shift; evaluating the luminous efficiency of the green and red devices by using the current efficiency; for the color change of the green light and the red light devices, the CIEx value is mainly used for evaluating, the increase of the CIEx indicates the red shift of the luminescence, and the decrease of the CIEx indicates the blue shift of the luminescence.
TABLE 1 comparison of component Properties in examples and comparative examples
Figure BDA0002893542300000381
Figure BDA0002893542300000391
In the blue light device of the compound 1-1, when the thickness of the light extraction layer is increased from 50nm to 90nm, the blue light index is changed from 92 to 76, the blue light index is reduced by 16, the CIEy is changed from 0.050 to 0.070, and the CIEy is increased by 0.020, which indicates that the blue light is red-shifted, meaning that the color of the blue light is lighter; the blue light device of the compound LEM-1 has the advantages that when the thickness of a light extraction layer is increased from 50nm to 90nm, the blue light index is changed from 96 to 83, only 7 is reduced, and the CIEy is changed from 0.051 to 0.063, and is increased by only 0.012; and, when the light extraction layer thicknesses are the same, the blue light indexes of the compounds 1-1 are all smaller than that of the compound LEM-1, and the CIEy of the compounds 1-1 is all larger than that of the compound LEM-1, indicating that the blue light color saturation of the blue light device of LEM-1 is higher.
In the green light device of the compound 1-1, the thickness of a light extraction layer is increased from 50nm to 90nm, the current efficiency is changed from 97cd/A to 101cd/A and is increased by 4cd/A, and the CIEx is changed from 0.235 to 0.250 and is increased by 0.015; while the current efficiency of the green device of compound LEM-1 was changed from 99cd/A to 106cd/A, which increased by 7cd/A, and CIEx was changed from 0.234 to 0.243, which increased by only 0.009.
The red light device of the compound 1-1 has the light extraction layer thickness increased from 50nm to 90nm, the current efficiency changed from 46cd/A to 53cd/A, only 7cd/A, and the CIEx changed from 0.665 to 0.675, and 0.010 increased; and the current efficiency of the red light device of the compound LEM-1 is changed from 48cd/A to 61cd/A, which is increased by 13cd/A, and the current efficiency of the compound LEM-1 is changed from 0.665 to 0.676, which is increased by 0.011.
As can be seen from the comparison of the devices with the same light-emitting color and different thicknesses of the compound 1-1 and the LEM-1, the compound LEM-1 as a light extraction material can enable the light-emitting color of the devices to have higher saturation and higher current efficiency compared with the compound 1-1 as a light extraction material.
Examples 40-46 use the compounds provided herein as a hole injection material and an electron transport material, respectively, and blue devices using these materials show a significant increase in blue light index and a decrease in CIEy, as compared to comparative examples of the same light extraction layer thickness.
TABLE 2 relative refractive index (n) comparison
Figure BDA0002893542300000401
As can be seen from table 2, compared with compounds 1-1 and 1-2, when the compound provided by the present application is used in a light extraction layer of an organic electroluminescent device, refractive indexes of blue light, green light and red light are significantly improved, so that light extraction can be more effectively promoted, a high light extraction rate can be provided, and the light emitting efficiency of the organic electroluminescent device can be greatly improved.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (11)

1. An organic electroluminescent device comprising:
a substrate, an anode electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode electrode and a light extraction layer;
the light extraction layer includes a compound of formula (I):
Figure FDA0002893542290000011
wherein Ar is1And Ar2Each independently selected from H atom, deuterium atom, halogen, C6-C30Aryl or C of3-C30Each independently hydrogen atom on said aryl and heteroaryl groups may be substituted with Ra, each independently heteroatom on said heteroaryl group is selected from O, S and N, each independently Ra is selected from deuterium, halogen, C1-C6Alkyl, phenyl, biphenyl, terphenyl, or naphthyl;
L1、L2and L3Each independently selected from phenylene or pyridylene.
2. The organic electroluminescent device according to claim 1, wherein the L1、L2And L3Each independently selected from the group consisting of:
Figure FDA0002893542290000012
the attachment sites are indicated in the figure.
3. The organic electroluminescent device according to claim 1, wherein the Ar is1And Ar2Each independently selected from the group consisting of:
Figure FDA0002893542290000021
wherein the content of the first and second substances,
R1and R2Each independently selected from C1-C6Alkyl of (C)6-C12Aryl or C of3-C12The heteroaryl group of (a).
4. The organic electroluminescent device according to claim 1, wherein the compound may be selected from the following compounds:
Figure FDA0002893542290000031
Figure FDA0002893542290000041
5. the organic electroluminescent device of claim 1, wherein the light extraction layer has a refractive index > 1.85.
6. The organic electroluminescent device according to claim 1, wherein the light extraction layer has a refractive index of red light of 1.85 or more, a refractive index of green light of 1.90 or more, and a refractive index of blue light of 2.00 or more.
7. The organic electroluminescent device according to claim 1, wherein the thickness of the light extraction layer is 50-90 nm.
8. The organic electroluminescent device according to claim 1, wherein the thickness of the light extraction layer is 60-80 nm.
9. The organic electroluminescent device of claim 1, wherein the hole transport layer comprises a compound of formula (II):
Figure FDA0002893542290000042
wherein the content of the first and second substances,
Ar3and Ar4Each independently selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rb;
R3-R6each independently selected from hydrogen, deuterium, C1-C10Alkyl of (C)3-C6Cycloalkyl of, C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rb, said R3-R6Wherein two adjacent groups can be connected to form a ring;
R7and R8Each independently selected from C1-C10Alkyl of (C)3-C6Cycloalkyl of, C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rb, said R7And R8Can be connected into a ring;
x is selected from O, S, CR9R10、NR11，R9And R10Each independently selected from C1-C10Alkyl of (C)3-C6Cycloalkyl of, C6-C30Aryl or C of3-C30The heteroaryl of (A), the R11Is selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rb, said R9And R10Can be connected into a ring;
l is selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene of (a), wherein the hydrogen atoms on the arylene and heteroarylene, independently of each other, may be substituted with Rb;
each heteroatom on the heteroaryl or heteroarylene is independently selected from O, S, N;
each Rb is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
10. The organic electroluminescent device according to claim 1, wherein the electron transport layer comprises a compound of formula (III):
Figure FDA0002893542290000051
wherein the content of the first and second substances,
R12-R17each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rc, and R12-R14Wherein two adjacent groups can be linked to form a ring, and R16And R17Can be connected into a ring;
a is selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Rc;
y is selected from O, S, CR18R19，R18And R19Each independently selected from C1-C6Alkyl of (C)5-C20Cycloalkyl of, C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rc, and R18And R19Can be connected into a ring;
X1-X4each independently selected from CR20Or N, R20Selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Rc, and adjacent R20Can be connected into a ring;
L1and L2Each independently selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Rc;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from O, S, N;
each Rc is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
11. A display device comprising the organic electroluminescent device according to any one of claims 1 to 10.
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