CN112952020A - Organic electroluminescent device and display device comprising same - Google Patents
Organic electroluminescent device and display device comprising same Download PDFInfo
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- CN112952020A CN112952020A CN202110149139.2A CN202110149139A CN112952020A CN 112952020 A CN112952020 A CN 112952020A CN 202110149139 A CN202110149139 A CN 202110149139A CN 112952020 A CN112952020 A CN 112952020A
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- organic electroluminescent
- reaction
- electroluminescent device
- light extraction
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- 150000001875 compounds Chemical class 0.000 claims abstract description 38
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
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- 235000010290 biphenyl Nutrition 0.000 claims description 3
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
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- 229910052731 fluorine Inorganic materials 0.000 claims description 3
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- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical group FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 12
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- BBVQDWDBTWSGHQ-UHFFFAOYSA-N 2-chloro-1,3-benzoxazole Chemical compound C1=CC=C2OC(Cl)=NC2=C1 BBVQDWDBTWSGHQ-UHFFFAOYSA-N 0.000 description 4
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- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 2
- ZSKXYSCQDWAUCM-UHFFFAOYSA-N 1-(chloromethyl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCl ZSKXYSCQDWAUCM-UHFFFAOYSA-N 0.000 description 2
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- XTHKRYHULUJQHN-UHFFFAOYSA-N 6-bromopyridin-3-amine Chemical compound NC1=CC=C(Br)N=C1 XTHKRYHULUJQHN-UHFFFAOYSA-N 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SAODOTSIOILVSO-UHFFFAOYSA-N 2-(4-bromophenyl)naphthalene Chemical compound C1=CC(Br)=CC=C1C1=CC=C(C=CC=C2)C2=C1 SAODOTSIOILVSO-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
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- ICMMJWDNKMITSS-UHFFFAOYSA-N dibenzothiophen-2-amine Chemical compound C1=CC=C2C3=CC(N)=CC=C3SC2=C1 ICMMJWDNKMITSS-UHFFFAOYSA-N 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
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- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/649—Aromatic compounds comprising a hetero atom
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Abstract
An organic electroluminescent device comprising a light extraction layer comprising a compound of 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.
Description
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.
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 light extraction layer comprising a compound of general formula (I):
wherein,
Ar1selected from C unsubstituted or substituted by Ra6-C50Aryl of (2), C unsubstituted or substituted by Ra2-C50The heteroaryl group of (a);
L1、L2and L3Each independently selected from the group consisting of a single bond, C unsubstituted or substituted by Ra6-C50Arylene of, unsubstituted or substituted by Ra C2-C50At least one of heteroarylenes of (a);
the heteroatoms on the heteroaryl and the heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from hydrogen, deuterium, fluorine, cyano, C1-C6Alkyl of (C)6-C18Aryl of (C)2-C18A heteroaryl, phenyl, biphenyl, terphenyl, or naphthyl 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.
Drawings
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 embodiments of the present application will be described clearly and completely with reference to the accompanying drawings, and it is obvious 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 light extraction layer comprising a compound of general formula (I):
wherein,
Ar1selected from C unsubstituted or substituted by Ra6-C50Aryl of (2), C unsubstituted or substituted by Ra2-C50The heteroaryl group of (a);
L1、L2and L3Each independently selected from the group consisting of a single bond, C unsubstituted or substituted by Ra6-C50Arylene of, unsubstituted or substituted by Ra C2-C50At least one of heteroarylenes of (a);
the heteroatoms on the heteroaryl and the heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from hydrogen, deuterium, fluorine, cyano, C1-C6Alkyl of (C)6-C18Aryl of (C)2-C18A heteroaryl, phenyl, biphenyl, terphenyl, or naphthyl group.
Preferably, Ar1Selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra2-C30The heteroaryl group of (a);
preferably, L1、L2And L3Each independently selected from the group consisting of a single bond, C unsubstituted or substituted by Ra6-C30Arylene of, unsubstituted or substituted by Ra C2-C30At least one of heteroarylenes of (a).
More preferably, Ar1Selected from C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra2-C18The heteroaryl group of (a);
more preferably, L1、L2And L3Each independently selected from the group consisting of a single bond, C unsubstituted or substituted by Ra6-C18Arylene of, unsubstituted or substituted by Ra C2-C18At least one of heteroarylenes of (a).
Still more preferably, Ar is1Selected from the following groups:
R1、R2and R3Each independently selected from C1-C6Alkyl of (C)6-C12Aryl or C of2-C12The heteroaryl group of (a);
still more preferably, said L1、L2And L3Each independently selected from the group consisting of:
for example, the Ar1Selected from the following groups:
R1、R2and R3Each independently selected from C1-C6Alkyl of (C)6-C12Aryl or C of3-C12The heteroaryl group of (a);
for example, the L1、L2And L3Each independently selected from the group consisting of:
for example, the compound of formula (I) may be selected from the following compounds:
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 having a high work function (4 e)V or greater 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:
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.
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:
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:
in a preferred embodiment, the green host material may be selected from at least one of the following GPH-1 to GPH-82 compounds:
in a preferred embodiment, the red host material may be selected from at least one of the following RH-1 to RH-10 compounds:
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.
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. For example, the material of the electron transport layer 6 may be selected from at least one of the following ET-1 to ET-58 compounds:
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:
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 > 1.88.
In some embodiments of the present application, the light extraction layer has a refractive index for red light of ≥ 1.89, a refractive index for green light of ≥ 1.98, and a refractive index for blue light of ≥ 2.03.
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、Cs2CO3At least one of BaO, 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 examples:
synthesis example 1: synthesis of Compound LEM-1
Into a reaction flask were charged 100mmol of 2-bromonaphthalene, 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)4The amount of (B) added is 1 mol% of 2-bromonaphthalene.
Into a reaction flask were charged 100mmol of 4-aminobiphenyl, 200mmol of M1, 28.8g of sodium tert-butoxide (300mmol), 800ml of xylene, and 1 mol% of palladium (dibenzylideneacetone) (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-1. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ8.32–7.82(m,7H),7.69(d,J＝10.0Hz,5H),7.60(d,J＝8.4Hz,1H),7.57(d,J＝12.0Hz,3H),7.49(s,1H),7.43–7.31(m,6H).
Synthesis example 2: synthesis of Compound LEM-2
Into a reaction flask were charged 100mmol of 2-chlorobenzoxazole, 100mmol of pinacol ester 4-aminophenylboronic 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, and cooling the reactants toAt room temperature, water was added, the 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 2-chlorobenzoxazole.
Into a reaction flask were charged 100mmol of p-chlorobromobenzene, 100mmol of 2-naphthylboronic 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 M2. Wherein, Pd (PPh)3)4The amount of (b) added is 1 mol% of p-chlorobromobenzene.
Into a reaction flask were charged 100mmol of M1, 200mmol of M2, 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. 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-2. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ8.32–7.82(m,8H),7.76–7.63(m,6H),7.61(s,2H),7.57(d,J＝12.0Hz,6H),7.38(d,J＝8.0Hz,8H).
Synthetic example 3: synthesis of Compound LEM-3
Into a reaction flask were charged 100mmol of 3-bromo-N-phenylcarbazole, 100mmol of pinacol 4-aminophenylborate, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh)3)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(PPh3)4The amount of the compound (b) added is 1 mol% of 3-bromo-N-phenylcarbazole.
Into a reaction flask were charged 100mmol of 2-bromonaphthalene, 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 M2. Wherein, Pd (PPh)3)4The amount of (B) added is 1 mol% of 2-bromonaphthalene.
Into a reaction flask were charged 100mmol of M1, 200mmol of M2, 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. 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)δ8.21(s,1H),8.21–8.04(m,4H),7.99(s,2H),7.91–7.69(m,5H),7.62(d,J＝8.0Hz,2H),7.57(d,J＝12.0Hz,6H),7.50(s,2H),7.38(t,J＝7.6Hz,6H),7.19(d,J＝10.0Hz,2H).
Synthetic example 4: synthesis of Compound LEM-4
Into a reaction flask were charged 100mmol of 2-bromo-5-chloropyridine, 100mmol of phenylboronic 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)4The amount of (B) added was 1 mol% based on the amount of 2-bromo-5-chloropyridine.
Into a reaction flask were charged 100mmol of 2-bromo-5-aminopyridine, 100mmol of 2-naphthaleneboronic 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 M2. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the amount of 2-bromo-5-aminopyridine.
Into a reaction flask were charged 100mmol of M1, 100mmol of M2, 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 M3. Wherein Pd (dba) is added in an amount of 1 mol% based on M2.
To a reaction flask were added 100mmol of M3, 100mmol of 2- (4-bromophenyl) -naphthalene, 28.8g sodium tert-butoxide (300mmol), 800ml xylene, and 1 mol% Pd (dba). 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-4. Wherein Pd (dba) is added in an amount of 1 mol% based on M3.
1H NMR(400MHz,Chloroform)δ8.85(s,1H),8.54–8.09(m,3H),8.08(s,1H),8.08(d,J＝12.0Hz,4H),8.02(s,1H),7.94(t,J＝10.0Hz,4H),7.66(t,J＝8.4Hz,1H),7.61–7.47(m,8H),7.38(d,J＝8.0Hz,3H),6.82(s,1H).
Synthesis example 5: synthesis of Compound LEM-5
Into a reaction flask were charged 100mmol of 2-chlorobenzoxazole, 100mmol of pinacol ester 4-aminophenylboronic 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 2-chlorobenzoxazole.
Into a reaction flask were charged 100mmol of 2-bromo-5-chloropyridine, 100mmol of 2-naphthaleneboronic 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 M2. Wherein, Pd (PPh)3)4The amount of (B) added was 1 mol% based on the amount of 2-bromo-5-chloropyridine.
Into a reaction flask were charged 100mmol of M1, 200mmol of M2, 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. 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-5. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ8.85(s,2H),8.37(s,2H),8.03(d,J＝10.0Hz,6H),8.00(s,3H),7.92(d,J＝10.0Hz,5H),7.73(d,J＝8.0Hz,4H),7.62(d,J＝8.0Hz,4H),7.57(s,1H),7.38(d,J＝8.0Hz,4H),6.82(s,2H).
Synthetic example 6: synthesis of Compound LEM-6
Into a reaction flask were charged 100mmol of 3-bromo-N-phenylcarbazole, 100mmol of pinacol 4-aminophenylborate, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh)3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping the reaction after the reaction is finishedAnd the reaction was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give white powder M1. Wherein, Pd (PPh)3)4The amount of the compound (b) added is 1 mol% of 3-bromo-N-phenylcarbazole.
Into a reaction flask were charged 100mmol of 2-bromo-5-chloropyridine, 100mmol of 2-naphthaleneboronic 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 M2. Wherein, Pd (PPh)3)4The amount of (B) added was 1 mol% based on the amount of 2-bromo-5-chloropyridine.
Into a reaction flask were charged 100mmol of M1, 200mmol of M2, 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. 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-6. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ8.85(s,2H),8.37(s,2H),8.29–8.04(m,6H),7.86(dd,J＝10.0,8.0Hz,7H),7.53(ddd,J＝10.0,8.8,7.2Hz,6H),7.38(d,J＝12.0Hz,3H),7.37–7.26(m,1H),7.19(d,J＝10.0Hz,2H),6.82(s,2H).
Synthetic example 7: synthesis of Compound LEM-42
Into a reaction flask were charged 100mmol of 2, 7-dibromodibenzothiophene, 100mmol of 1-naphthalene boronic 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 70 ℃ for 3 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, and concentrating an organic phase to obtain whiteThe solid was filtered, washed with water and the solid obtained was purified by recrystallization from toluene to give M1 as a white powder. Wherein, Pd (PPh)3)4The amount of (B) is 1 mol% based on the amount of 2, 7-dibromodibenzothiophene.
A reaction flask was charged with 200mmol of M1, 100mmol of 2-amino-dibenzothiophene, 28.8g sodium tert-butoxide (300mmol), 800ml xylene, and 1 mol% Pd (dba) was 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-42. Wherein Pd (dba) is added in an amount of 1 mol% based on M1.
1H NMR(400MHz,Chloroform)δ8.95(s,2H),8.61–8.36(m,5H),8.12(s,2H),7.99(s,2H),7.96–7.74(m,7H),7.62–7.53(m,7H),7.40(s,2H),7.33(d,J＝12.0Hz,3H),7.01(s,3H).
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:
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 BD01, evaporation is carried out by 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 BD01 is 3% of the evaporation rate of the main material, the total film thickness of evaporation is 20nm, and the main material and the luminescent dye are respectively the following materials:
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:
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.
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.
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 33
The same procedure as in the previous examples, except that LEM-1 was replaced with LEM-2, LEM-3, LEM-4, LEM-5, LEM-6 and LEM-42, respectively, was repeated except that the thickness of the extraction layer was 70nm, as shown in Table 1.
The data and test results for examples 1-33 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.
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.
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 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
TABLE 2 relative refractive index (n) comparison
As can be seen from table 1, with respect to the blue device, for compound 1-1, when the light extraction layer thickness was increased from 50nm to 90nm, the blue light index was changed from 92 to 76, decreased by 16, CIEy was changed from 0.050 to 0.070, increased by 0.020, indicating that the blue light was red-shifted and the color was lighter; whereas for compound LEM-1, when the thickness of the light extraction layer was increased from 50nm to 90nm, the blue light index was changed from 97 to 84, which was only decreased by 13, and CIEy was changed from 0.043 to 0.049, which was only increased by 0.006, and when the thickness of the light extraction layer was the same, the blue light index of compound 1-1 was smaller than that of compound LEM-1, and the CIEy of compound 1-1 was larger than that of compound LEM-1. Indicating that the blue color saturation of the blue device of LEM-1 is higher.
Regarding the green device, for compound 1-1, the light extraction layer thickness increased from 50nm to 90nm, the current efficiency changed from 97cd/A to 101cd/A, only 4cd/A, CIEx changed from 0.235 to 0.250, 0.015; whereas for compound LEM-1, the current efficiency changed from 136cd/a to 147cd/a, an increase of 11cd/a, CIEx changed from 0.345 to 0.353, an increase of only 0.008. Indicating that the green color saturation of the green device of LEM-1 is higher and the current efficiency is greater.
Regarding the red light device, for compound 1-1, the light extraction layer thickness was increased from 50nm to 90nm, the current efficiency was changed from 46cd/A to 53cd/A, which was only increased by 7cd/A, and the CIEx was changed from 0.665 to 0.675, which was increased by 0.010; whereas for compound LEM-1, the current efficiency changed from 47cd/a to 60cd/a, increasing by 13cd/a, CIEx changed from 0.661 to 0.672, increasing by only 0.011. It shows that the red light color saturation of the red light device of LEM-1 is higher and the current efficiency is larger.
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, compared with the compound 1-1 as the material of the light extraction layer, the compound LEM-1 as the material of the light extraction layer can ensure that the light-emitting color of the device has higher saturation and higher current efficiency.
Examples 16-18, 19-21, 22-24, 25-27, 28-30, 31-33 used LEM-2, LEM-3, LEM-4, LEM-5, LEM-6, LEM-42, respectively, as light extraction layer materials. Compared with the compound 1-1 as a light extraction layer material, the organic electroluminescent device using the compound as the light extraction layer material has higher luminous color saturation and higher current efficiency.
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 light extraction layer comprising a compound of formula (I):
wherein,
Ar1selected from C unsubstituted or substituted by Ra6-C50Aryl of (2), C unsubstituted or substituted by Ra2-C50The heteroaryl group of (a);
L1、L2and L3Each independently selected from the group consisting of a single bond, C unsubstituted or substituted by Ra6-C50Arylene of, unsubstituted or substituted by Ra C2-C50At least one of heteroarylenes of (a);
the heteroatoms on the heteroaryl and the heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from hydrogen, deuterium, fluorine, cyano, C1-C6Alkyl of (C)6-C18Aryl of (C)2-C18A heteroaryl, phenyl, biphenyl, terphenyl, or naphthyl group.
2. The organic electroluminescent device according to claim 1,
Ar1selected from C unsubstituted or substituted by Ra6-C30Aryl of (2), C unsubstituted or substituted by Ra2-C30The heteroaryl group of (a);
L1、L2and L3Each independently selected from the group consisting of a single bond, C unsubstituted or substituted by Ra6-C30Arylene of, unsubstituted or substituted by Ra C2-C30At least one of heteroarylenes of (a).
3. The organic electroluminescent device according to claim 1,
Ar1selected from C unsubstituted or substituted by Ra6-C18Aryl of (2), C unsubstituted or substituted by Ra2-C18The heteroaryl group of (a);
L1、L2and L3Each independently selected from the group consisting of a single bond, C unsubstituted or substituted by Ra6-C18Arylene of, unsubstituted or substituted by Ra C2-C18At least one of heteroarylenes of (a).
4. The organic electroluminescent device according to claim 1, wherein the Ar is1Selected from the following groups:
R1、R2and R3Each independently selected from C1-C6Alkyl of (C)6-C12Aryl of (2)Or C2-C12The heteroaryl group of (a);
said L1、L2And L3Each independently selected from the group consisting of:
5. the organic electroluminescent device according to claim 1, wherein the Ar is1Selected from the following groups:
R1、R2and R3Each independently selected from C1-C6Alkyl of (C)6-C12Aryl or C of3-C12The heteroaryl group of (a);
said L1、L2And L3Each independently selected from the group consisting of:
6. the organic electroluminescent device according to claim 1, wherein the compound of formula (I) may be selected from the following compounds:
7. the organic electroluminescent device of claim 1, wherein the light extraction layer has a refractive index > 1.88.
8. The organic electroluminescent device according to claim 1, wherein the light extraction layer has a refractive index of red light of 1.89 or more, a refractive index of green light of 1.98 or more, and a refractive index of blue light of 2.03 or more.
9. The organic electroluminescent device according to claim 1, wherein the thickness of the light extraction layer is 50-90 nm.
10. The organic electroluminescent device according to claim 1, wherein the thickness of the light extraction layer is 60-80 nm.
11. A display device comprising the organic electroluminescent device according to any one of claims 1 to 10.
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| CN114805295A (en) * | 2022-05-20 | 2022-07-29 | 江苏南大光电材料股份有限公司 | Method for purifying halogenated dibenzothiophene compound |
| CN114853701A (en) * | 2022-05-25 | 2022-08-05 | 吉林奥来德光电材料股份有限公司 | Luminescent auxiliary material and preparation method and application thereof |
| WO2022166623A1 (en) * | 2021-02-03 | 2022-08-11 | 烟台显华光电材料研究院有限公司 | Organic electroluminescent device and display apparatus having same |
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| CN110577471A (en) * | 2018-06-11 | 2019-12-17 | 乐金显示有限公司 | electroluminescent compounds and electroluminescent devices comprising the same |
| CN111995530A (en) * | 2019-05-27 | 2020-11-27 | 东进世美肯株式会社 | Organic compound for capping layer and organic light emitting device including the same |
| CN111995532A (en) * | 2019-05-27 | 2020-11-27 | 东进世美肯株式会社 | Organic compound for capping layer and organic light emitting device including the same |
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| CN112952020B (en) * | 2021-02-03 | 2024-06-18 | 烟台显华光电材料研究院有限公司 | Organic electroluminescent device and display device comprising same |
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| CN110577471A (en) * | 2018-06-11 | 2019-12-17 | 乐金显示有限公司 | electroluminescent compounds and electroluminescent devices comprising the same |
| CN111995530A (en) * | 2019-05-27 | 2020-11-27 | 东进世美肯株式会社 | Organic compound for capping layer and organic light emitting device including the same |
| CN111995532A (en) * | 2019-05-27 | 2020-11-27 | 东进世美肯株式会社 | Organic compound for capping layer and organic light emitting device including the same |
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| WO2022166623A1 (en) * | 2021-02-03 | 2022-08-11 | 烟台显华光电材料研究院有限公司 | Organic electroluminescent device and display apparatus having same |
| CN114805295A (en) * | 2022-05-20 | 2022-07-29 | 江苏南大光电材料股份有限公司 | Method for purifying halogenated dibenzothiophene compound |
| CN114853701A (en) * | 2022-05-25 | 2022-08-05 | 吉林奥来德光电材料股份有限公司 | Luminescent auxiliary material and preparation method and application thereof |
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