CN113013343B - Organic electroluminescent device, method of manufacturing the same, and display apparatus including the same - Google Patents

Organic electroluminescent device, method of manufacturing the same, and display apparatus including the same Download PDF

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CN113013343B
CN113013343B CN201911328099.7A CN201911328099A CN113013343B CN 113013343 B CN113013343 B CN 113013343B CN 201911328099 A CN201911328099 A CN 201911328099A CN 113013343 B CN113013343 B CN 113013343B
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CN113013343A (en
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王芳
张小庆
张兆超
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Jiangsu Sunera Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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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
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    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention aims to provide an organic electroluminescent device, which is sequentially provided with a substrate, a first electrode, an organic layer and a second electrode from bottom to top, wherein the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, the second electrode is an anode, the organic layer comprises an emission layer, the emission layer comprises a host material and a doping material, the host material comprises a first organic compound and a second organic compound, and the first organic compound is a compound represented by a general formula (1) or a general formula (2):
Figure DDA0002328899210000011
wherein the second organic compound is a compound described by the general formula (3):
Figure DDA0002328899210000012

Description

Organic electroluminescent device, method of manufacturing the same, and display apparatus including the same
Technical Field
The invention relates to the technical field of photoelectric devices. More particularly, the present invention relates to an organic electroluminescent device, especially an organic electroluminescent device comprising an emissive layer. The invention also relates to a method for preparing the organic electroluminescent device and a display device comprising the organic electroluminescent device.
Background
The organic electroluminescent device is a self-emission device having a wide viewing angle, a high contrast ratio, a short response time, and good luminance, driving voltage, and response speed characteristics. The organic electroluminescent device produces a full color image.
The organic electroluminescent device includes an anode, a cathode, and an organic layer including an emission layer disposed between the anode and the cathode, wherein the organic layer is a general term for each layer between the cathode and the anode. In addition, a hole transport region may exist between the anode and the emission layer, and an electron transport region may exist between the emission layer and the cathode. Holes from the anode may migrate through the hole transport region to the emissive layer, and electrons from the cathode may migrate through the electron transport region to the emissive layer. Carriers (e.g., holes and electrons) recombine in the emissive layer to generate excitons. When the excitons drop from an excited state to a ground state, light is emitted.
In order to improve the efficiency, stability and lifetime of organic electroluminescent devices, device structure improvement and new material development must be performed to meet the requirements of future flat panel displays. Therefore, there is a need to develop materials for organic electroluminescent devices having more excellent properties.
Disclosure of Invention
The invention aims to provide an organic electroluminescent device, which is sequentially provided with a substrate, a first electrode, an organic layer and a second electrode from bottom to top, wherein the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, the second electrode is an anode, the organic layer comprises an emission layer, the emission layer comprises a host material and a doping material, the host material comprises a first organic compound and a second organic compound, and the first organic compound is a compound described by a general formula (1) or a general formula (2):
Figure GDA0003709648560000011
the second organic compound is a compound represented by the general formula (3):
Figure GDA0003709648560000012
wherein, X, X 1 、X 2 、X 2 ' independently represent a single bond, an oxygen atom, a sulfur atom, C (R) 5 )(R 6 ) Or N (R) 7 )；
i. m and n are respectively and independently 0 or 1;
ar and Ar' represent substituted or unsubstituted C 6-30 An arylene, or a substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms selected from N, O and S;
R 1 、R 2 each independently represents a hydrogen atom, a deuterium atom, a cyano group, a halogen, C 1-30 Alkyl, alkoxy, aryloxy, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms selected from N, O and S, C 6-30 Aryl or-N (A1) (A2);
each Z is independently represented by a nitrogen atom or C (R) 8 ) (ii) a Each Z' is independently represented by a nitrogen atom or C (R) 8 ') to a host; z, Z' at the attachment site is represented as a carbon atom;
each Z 1 Are all independently represented by a nitrogen atom or C (R) 9 ) (ii) a Z at the point of attachment 1 Represented as a carbon atom;
r in the general formula (2) 3 Or R 4 A possible attachment site;
R 3 、R 4 represented by a hydrogen atom, a structure represented by the general formula (4) or the general formula (5), and R 3 、R 4 Not simultaneously represented as a hydrogen atom;
Figure GDA0003709648560000021
wherein, the general formula (4) and the general formula (5) are respectively connected with the adjacent Z marked in the general formula (2) through the adjacent position marked by 1 Are connected in a ring; said X 3 、X 4 Each independently represents a single bond, an oxygen atom, a sulfur atom, C (R) 10 )(R 11 ) Or N (R) 12 ) (ii) a And X 3 、X 4 Not simultaneously represent a single bond;
each Z 2 Independently represent a nitrogen atom or C (R) 13 ) (ii) a Z at the point of attachment 2 Represents a carbon atom;
b represents a structure represented by general formula (6), general formula (7), general formula (8), general formula (9), general formula (10), general formula (11), general formula (12), general formula (13), general formula (14) or general formula (15);
Figure GDA0003709648560000022
wherein "-" in the general formulae (6) to (15) represents a linking site to Ar' in the general formula (3);
A、X 5 each independently represents a single bond, an oxygen atom, a sulfur atom, C (R) 14 )(R 15 ) Or N (R) 16 )；
a represents 0 or 1;
each Z 3 Each Z 4 Each independently represents a nitrogen atom or C (R) 17 ) (ii) a Z at the point of attachment 3 、Z 4 Represents a carbon atom;
q represents N atom or C-H, and at least one Q represents nitrogen atom;
Q 1 、Q 2 、Ar 1 each independently represents substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms selected from N, S and O;
R a 、R b 、R c 、R d 、R e 、R f each independently represents substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted 5 to 30 membered heteroaryl containing one or more heteroatoms selected from N, S and O;
R 5 -R 7 、R 10 -R 12 、R 14 -R 16 are each independently represented by C 1-6 Alkyl, or substituted or unsubstituted C 6-30 An aryl group;
R 8 、R 8 ’、R 9 、R 13 、R 17 each independently represents a hydrogen atom, deuterium, cyano, alkoxy, halogen, C 1-30 Alkyl, aryloxy, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms, C 6-30 Aryl or-N (A3) (a 4);
wherein A1 to A4 each independently represents substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted containing one or more heteroatoms selected from N, O and SA 5-to 30-membered heteroaryl;
in the above radical definitions, the substituents are optionally selected from deuterium atoms, cyano groups, alkoxy groups, aryloxy groups, C 1-30 Alkyl, substituted or unsubstituted C 6-30 One or more of aryl, or substituted or unsubstituted 5-to 30-membered heteroaryl containing one or more heteroatoms.
The present invention is also directed to a method of preparing the above organic electroluminescent device, comprising sequentially laminating a first electrode, an organic layer and a second electrode on a substrate.
It is also an object of the present invention to provide a display apparatus including the above organic electroluminescent device.
The organic electroluminescent device of the present invention comprising the above-described emission layer has improved efficiency and lifetime. Therefore, the organic electroluminescent device provided by the invention has good application effect and industrialization prospect.
Drawings
The invention is further illustrated by means of the attached drawings, the content of which is not in any way limiting.
Fig. 1 shows a basic structure of an organic electroluminescent device of the present invention, in which:
10. organic electroluminescent device
190. Second electrode
150. Organic layer
110. A first electrode
Detailed Description
The invention will be described in more detail hereinafter with reference to the accompanying drawings, without intending to limit the invention thereto.
In the present invention, unless otherwise specified, all operations are carried out under ambient temperature and pressure conditions.
It should be understood that, in describing the electrode and the organic electroluminescent device of the present invention, and other structures, terms such as "upper", "lower", "top" and "bottom" used to indicate orientation, merely indicate orientation in a certain specific state, and do not mean that the relevant structure can exist only in the orientation; conversely, if the structure is repositioned, e.g., inverted, the orientation of the structure is changed accordingly. Specifically, in the present invention, the "bottom" side of the electrode refers to the side of the electrode that is closer to the substrate during fabrication, while the opposite side that is further from the substrate is the "top" side.
It will be understood that the terms "comprises" and/or "comprising," when used, specify the presence of stated features or components, but do not preclude the presence or addition of one or more other features or components.
As used herein, "X comprises a first organic compound" may be interpreted as "X may comprise one type(s) of the first organic compound of formula (1) or two different types(s) of the first organic compound of formula (1)". Similarly, "X includes a second organic compound" may be interpreted as "X may include one type (kind) of the second organic compound of formula (3) or two types (kinds) of different second organic compounds of formula (3)".
As used herein, the term "organic layer" refers to a single layer and/or a plurality of layers located between a first electrode and a second electrode in an organic electroluminescent device. The material included in the organic layer is not limited to an organic material.
C as used herein 1-30 Alkyl refers to a straight or branched chain aliphatic monovalent hydrocarbon group having 1 to 30 carbon atoms in the main chain. In this context, it is preferred to use C 2-10 Alkyl, more preferably C 3-6 An alkyl group. Non-limiting examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. C as used herein 1-30 Alkylene means with C 1-30 The alkyl groups have divalent groups of the same structure. In particular, C as used herein 1-6 Alkyl refers to a straight or branched chain aliphatic monovalent hydrocarbon group having 1 to 6 carbon atoms in the main chain. In this context, preference is given to using methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl or hexyl.
Alkoxy as used herein refers to a compound represented by-OA 101 (wherein A101 is C) 1-60 Alkyl) monovalent group. In this context, it is preferred to use C 2-10 Alkoxy, more preferably C 3-6 An alkoxy group. Non-limiting examples thereof mayTo include methoxy, ethoxy and isopropoxy.
C as used herein 6-30 Aryl means a monovalent group comprising a carbocyclic aromatic system having from 6 to 30 carbon atoms as ring-forming atoms, C as used herein 6-30 Arylene refers to a divalent group comprising a carbocyclic aromatic system having from 6 to 30 carbon atoms as ring-forming atoms. In this context, it is preferred to use C 5-10 Aryl or arylene radicals, more preferably C 6-8 Aryl or arylene. Non-limiting examples thereof may include phenyl, naphthyl, anthryl, phenanthryl, pyrenyl and
Figure GDA0003709648560000041
and (4) a base. When C is present 6-30 Aryl and/or C 6-30 When the arylene group includes two or more rings, the rings may be fused to each other.
The 5-to 30-membered heteroaryl group used herein means a monovalent group including a carbocyclic aromatic system having at least one hetero atom selected from N, O, P and S as a ring-forming atom and 1 to 30 carbon atoms. The 5-to 30-membered heteroarylene group used herein means a divalent group including a carbocyclic aromatic system having at least one hetero atom selected from N, O, P and S as a ring-constituting atom and 1 to 30 carbon atoms. In this context, it is preferred to use C 4-10 Heteroaryl or heteroarylene, more preferably C 5-8 Heteroaryl or heteroarylene. Non-limiting examples thereof may include pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl and isoquinolyl. When the 5-to 30-membered heteroaryl and 5-to 30-membered heteroarylene include two or more rings, these rings may be fused to each other.
Aryloxy as used herein refers to a compound represented by-OA 102 (wherein A102 is C) 6-30 Aryl), C as used herein 6-30 Arylthio means a compound represented by-SA 103 (wherein A103 is C 6-30 Aryl) group. Preferably, C is used herein 6-10 Aryloxy group, and C 6-10 An arylthio group.
As used herein, the expression "Ph" represents phenyl and the expression "halogen" represents fluorine, chlorine, bromine or iodine.
Fig. 1 schematically shows the basic structure of an organic electroluminescent device of the present invention.
Referring to fig. 1, the substrate may be disposed below the first electrode 110 or above the second electrode 190. The substrate may be any substrate commonly used in organic electroluminescent devices. For example, the substrate may be a glass substrate or a transparent plastic substrate having good mechanical strength, thermal stability, transparency, surface flatness, handling convenience, and water resistance, but is not limited thereto. The thickness of the substrate may range from 50 to 700 μm.
The first electrode 110 may be an anode and the second electrode 190 may be a cathode.
Alternatively, the first electrode 110 may be a cathode and the second electrode 190 may be an anode.
For example, the first electrode 110 may be formed on the substrate by depositing or sputtering a first electrode material. When the first electrode 110 is an anode, the first electrode material is preferably a material having a high work function so that holes are easily injected into the organic layer. Non-limiting examples of the first electrode material include, but are not limited to, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin oxide (SnO) 2 ) Zinc oxide (ZnO), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The first electrode 110 may have a single layer structure or a multi-layer structure including two or more layers. For example, the first electrode 110 may have a three-layer structure of ITO/Ag/ITO, but is not limited thereto. In addition, the thickness of the first electrode depends on the material used, and is generally 50-500nm, preferably 70-300nm and more preferably 100-200 nm.
An organic layer 150 including an emission layer is positioned on the first electrode 110. The organic layer 150 may further include a hole transport region between the first electrode 110 and the emission layer, and an electron transport region between the emission layer and the second electrode 190.
The hole transport region may include, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a buffer layer, and an Electron Blocking Layer (EBL); the electron transport region may include, but is not limited to, a charge control layer, and may further include a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), or an Electron Injection Layer (EIL).
The hole transport region may have a single-layer structure formed of a single material, a single-layer structure formed of a plurality of different materials, or a multi-layer structure having a plurality of layers formed of a plurality of different materials.
When the hole transport region includes a hole injection layer, the hole injection layer may be formed on the first electrode 110 by a method such as vacuum deposition, spin coating, casting, a langmuir-blodgett (LB) method, inkjet printing, laser printing, or Laser Induced Thermal Imaging (LITI).
When the hole injection layer is formed by vacuum deposition, it may be deposited at a deposition temperature of about 100-500 deg.C at about 10 deg.C, depending on the compound used to form the hole injection layer and the desired structure of the hole injection layer -8 -10 -3 Vacuum degree of tray and its combination
Figure GDA0003709648560000042
The deposition rate of (a) is vacuum deposition.
When the hole injection layer is formed by spin coating, the spin coating may be performed at a coating rate of about 2000-.
The material of the hole injection layer is generally a material preferably having a high work function so that holes are easily injected into the organic material layer. Specific examples of the material of the hole injection layer include, but are not limited to, copper phthalocyanine, N '-diphenyl-N, N' -bis- [4- (phenyl-m-tolylamino) -phenyl ] -biphenyl-4, 4 '-diamine (DNTPD), 4',4 ″ -tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (TDATA), 4',4 ″ -tris { N, - (2-naphthyl) -N-phenylamino } -triphenylamine (2TNATA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), Polyaniline/camphorsulfonic acid (PANI/CSA), (polyaniline)/poly (4-styrenesulfonate) (PANI/PSS), or HT23/NDP (specific structural formula will be shown below) in a mass ratio of 99:1, preferably 98:2, more preferably 97: 3. The thickness of the hole injection layer of the present invention may be 5 to 100nm, preferably 5 to 50nm and more preferably 5 to 20 nm.
When the hole transport region includes a hole transport layer, the hole transport layer may be formed on the first electrode 110 or the hole injection layer by a method such as vacuum deposition, spin coating, casting, an LB method, inkjet printing, laser printing, or LITI. When the hole transport layer is formed by vacuum deposition or spin coating, the deposition or coating conditions may be similar to those for forming the hole injection layer.
Specific examples of materials that can pass through the hole transport layer include, but are not limited to: carbazole-based derivatives such as N-phenylcarbazole or polyvinylcarbazole; a fluorene-based derivative; triphenylamine-based derivatives such as N, N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1, 1-biphenyl ] -4, 4' -diamine (TPD) and 4,4',4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), N ' -bis (1-naphthyl) -N, N ' -diphenyl benzidine (NPB), 4' -cyclohexylidene bis [ N, N-bis (4-methylphenyl) aniline ] (TAPC) and HT23 (specific structural formulae thereof will be shown below). According to the present invention, it is preferable to use HT23 as the hole transport layer material. The thickness of the hole transport layer of the present invention may be 5 to 200nm, preferably 10 to 150nm and more preferably 20 to 120 nm.
The hole transport region may include at least one compound selected from the group consisting of: for example, m-MTDATA, TDATA, 2-TNATA, NPB, β -NPB, TPD, spiro-NPB, methylated NPB, TAPC, HMTPD, 4',4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), (polyaniline)/poly (4-styrenesulfonate) (PANI/PSS), a compound represented by formula 201, and a compound represented by formula 202.
Figure GDA0003709648560000051
Figure GDA0003709648560000061
In the case of the equations 201 and 202,
L 201 to L 205 Independently of one another, are as defined herein for Ar or Ar';
xa 1 to xa 4 Independently of one another, are selected from 0, 1, 2 and 3;
xa 5 selected from 1, 2,3, 4 and 5; and
R 201 to R 204 Independently of one another as R in the present text 1 The definition of (1).
In particular embodiments, the compounds represented by formula 201 and formula 202 may include, independently of each other, the following compounds HT1 through HT25, but are not limited thereto:
Figure GDA0003709648560000062
Figure GDA0003709648560000071
the hole transport region may have a thickness of about
Figure GDA0003709648560000072
Within the range of, for example, about
Figure GDA0003709648560000073
Within the range of (1). When the hole transport region includes a hole injection layer and a hole transport layer, the hole injection layer may have a thickness of about
Figure GDA0003709648560000074
Figure GDA0003709648560000075
(for example,
Figure GDA0003709648560000076
or
Figure GDA0003709648560000077
) In the range of (a) to (b),for example, it may be in the range of about
Figure GDA0003709648560000078
In the range of (1), the hole transport layer may have a thickness of about
Figure GDA0003709648560000079
Within the range of, for example, about
Figure GDA00037096485600000710
Within the range of (1). When the thicknesses of the hole transporting region, the hole injecting layer, and the hole transporting layer are within any of the above ranges, satisfactory hole transporting properties can be obtained without significantly increasing the driving voltage.
In addition to the above materials, the hole transport region may further include a charge generation material to improve the conductive property. The charge generating material may be uniformly or non-uniformly dispersed in the hole transport region.
The charge generating material may be, for example, a p-dopant. The p-dopant may include at least one compound selected from the group consisting of: quinone derivatives, such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4-TCNQ); metal oxides such as tungsten oxide or molybdenum oxide; or cyano-containing compounds, such as the compounds HT-D1, NDP and F4-TCNQ shown below:
Figure GDA00037096485600000711
the hole transport region may include a buffer layer, an electron blocking layer, or a combination thereof, in addition to the hole injection layer and the hole transport layer. The buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus may improve light emitting efficiency of the organic electroluminescent device. The electron blocking layer may prevent electrons from being injected from the electron transport region. In particular embodiments, the electron blocking layer compounds include, but are not limited to, compounds EB1 through EB7 of the following:
Figure GDA00037096485600000712
the electron blocking layer of the present invention may have a thickness of 1 to 200nm, preferably 5 to 150nm, and more preferably 10 to 100 nm.
In one embodiment of the present invention, the emission layer may be formed on the first electrode 110 or on the hole transport region by a method such as vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, or laser induced thermal imaging. When the emission layer is formed by vacuum deposition or spin coating, the deposition and coating conditions for the emission layer may be similar to those for forming the hole injection layer.
When the organic electroluminescent device 10 is a full-color organic electroluminescent device, the emission layer may be patterned into a red emission layer, a green emission layer, or a blue emission layer, each of which corresponds to a sub-pixel. Optionally, the emission layer may emit white light, and may have a stacked structure of a red emission layer, a green emission layer, and a blue emission layer, or may include a red emission material, a green emission material, and a blue emission material mixed together in a single layer. Optionally, the emission layer may be a white emission layer, and may further include a color conversion layer or a color filter that converts white light into light of a desired color.
The emissive layer may include a host material and a guest material.
In one embodiment of the present invention, the host material in the emission layer may include a first organic compound described by general formula (1) or general formula (2):
Figure GDA0003709648560000081
and, a second organic compound represented by formula (3):
Figure GDA0003709648560000082
wherein, Z, Z' and Z 1 、X、X 1 、X 2 、X 2 ’、Ar、Ar’、R 1 -R 4 I, m, n and B and are as defined above.
In a preferred embodiment of the present invention, in the general formula (1), the general formula (2) and the general formula (3), Ar' independently represent the following groups substituted or unsubstituted with a substituent: phenylene, pentalenylene, indenylene, naphthylene, azulenylene, and spirofluorenyl groups, heptalenylene, indylene, acenaphthylene, fluorenylene, spirofluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenylene, phenanthrylene, anthrylene, benzo [9,10 ] ene]Phenanthrylene, pyrenylene
Figure GDA0003709648560000083
A group selected from the group consisting of a phenylene group, a tetracylene group, a picylene group, a peryleneene group, a pentylene group, a hexacrylene group, a pentacylene group, a rubicene group, a coronene group, an ovolene group, a pyrrolylene group, a thienylene group, a furanylene group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolylene group, an oxazolylene group, an isoxazolylene group, a pyridyl group, a pyrazinylene group, a pyrimidylene group, a pyridazinylene group, an isoindolylene group, an indolyl group, an indazolene group, a purinylene group, a quinolylene group, an isoquinolylene group, a benzoquinolylene group, an phthalazinylene group, a naphthyrylene group, a quinoxalylene group, an quinazolinylene group, a cinnolinylene group, a carbazolyl group, a phenanthridinylene group, an acridinylene group, a phenanthrolinylene group, a phenazinylene group, a benzimidazolylene group, a benzofuranylene group, a benzothiophenylene group, an isobenzothiazolyl group, a benzoxazolyl group, an isoxazolylene group, a triazolylene group, a tetrazolylene group, a, Oxadiazolyl, triazinyl, dibenzofuranylidene, dibenzothiophenylidene, benzocarbazolyl, or dibenzocarbazolyl groups;
R 1 、R 2 、R 8 、R 8 ’、R 12 、R 16 each independently represents the following group substituted or unsubstituted with a substituent: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, naphthyl, biphenylyl, terphenylyl, dimethylfluorenyl, diphenylfluorenyl, spiroFluorenyl, carbazolyl, dibenzothienyl, dibenzofuranyl, anthracyl, phenanthryl, benzophenanthrenyl, pyrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, carbazolyl, benzoquinolinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, benzimidazolyl, benzofuranyl, benzothienyl, triazolyl, triazinyl, imidazopyrimidinyl, pyridobenzofuranyl, pyrimidobenzofuranyl, pyridobenzothiophenyl, or dibenzodioxin;
R 5 -R 7 、R 9 -R 11 、R 13 -R 15 each independently represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, or a substituted or unsubstituted terphenyl group;
Q 1 、Q 2 、Ar 1 each independently represents the following group substituted or unsubstituted with a substituent: phenyl, naphthyl, biphenylyl, terphenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, dibenzothienyl, dibenzofuranyl, anthracenyl, phenanthrenyl, benzophenanthrenyl, pyrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, carbazolyl, benzoquinolinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, benzimidazolyl, benzofuranyl, benzothienyl, triazolyl, triazinyl, imidazopyrimidinyl, pyridobenzofuranyl, pyrimidophenyl, pyridobenzothiophenyl, pyrimidophenyl, thianthrenyl, phenoxathiyl, or dibenzodioxin;
R a 、R b 、R c 、R d 、R e 、R f each independently represents the following group substituted or unsubstituted with a substituent: phenyl, naphthyl, anthracenyl, pyrenyl, phenanthrenyl, fluorenyl, carbazolyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, dibenzofuranyl, or spirofluorenyl;
the substituents are selected from: deuterium, F, Cl, Br, I, cyano, amino, amidino, C 1 -C 20 Alkyl radical, C 1 -C 20 Alkoxy, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, phenyl, biphenyl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, indacenaphthenyl, acenaphthenyl, fluorenyl, spirofluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthryl, anthracenyl, fluoranthenyl, benzo [9,10 ] benzo]Phenanthryl, pyrenyl,
Figure GDA0003709648560000094
A group, a tetracenyl group, a picenyl group, a perylene group, an amylene group, a hexacenyl group, a pentaphenyl group, a rubicene group, a coronenyl group, an egg phenyl group, a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolyl group, isoquinolinyl, benzoquinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, benzimidazolyl, benzofuranyl, benzothienyl, isobenzothiazolyl, benzoxazolyl, isobenzooxazolyl, triazolyl, tetrazolyl, oxadiazolyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, benzocarbazolyl, dibenzocarbazolyl, thiadiazolyl, and/or imidazopyridinyl.
In a preferred embodiment of the present invention, the first organic compound may be represented by formula (1-1):
Figure GDA0003709648560000091
wherein,
Ar、X、X 2 、i、Z、Z 1 and R 3 As defined above; "+" represents R in formula (1-1) 3 Possible positions of the parallel ring connection with the rest; and is
The second organic compound is represented by formula (3):
Figure GDA0003709648560000092
wherein,
Ar’、Z’、B、n、X 2 ' is as defined above.
In a more preferred embodiment of the present invention, the first organic compound is a compound of formula (1-1), wherein R represents in formula (1-1) 3 Possible positions of the parallel ring connection with the rest;
(X) i is an oxygen atom, C (C) 1-6 Alkyl radical) 2 Or C (phenyl) 2 Preferably C (C) 1-6 Alkyl radical) 2 Is C (methyl) 2 ；
Each Z independently represents CH or C (C) 1-6 Alkyl), preferably C 1-6 Alkyl is tert-butyl, wherein Z at the point of attachment is a carbon atom;
ar is phenylene or a single bond;
X 2 is a single bond, C (phenyl) 2 Or C (C) 1-6 Alkyl radical) 2 Preferably, C 1-6 Alkyl is methyl, or
Figure GDA0003709648560000093
Wherein represents a site of attachment to the remainder of the structural formula;
each Z 1 Independently CH, wherein Z is at the point of attachment 1 Is a carbon atom;
R 3 is a hydrogen atom, N (phenyl) 2 Or a structure of the general formula (4) in which X is 3 Or X 4 Independently a single bond, C (C) 1-6 Alkyl radical) 2 N (phenyl) or N (biphenyl), preferably C 1-6 Alkyl is methyl, wherein the general formula (4) is represented by two adjacent Z's of the formula (1-1) and the symbol on the formula 1 Are connected in a ring;
each Z 2 Independently of each other, is a CH,
particularly preferably, the second organic compound is a compound represented by formula (3), wherein
Each Z' is independently CH, C (phenyl) or C (C) 1-6 Alkyl), preferably, C 1-6 Alkyl is tert-butyl, wherein Z' at the point of attachment is a carbon atom;
X 2 ' is an oxygen atom or a single bond;
n is 0 or 1;
ar' is a single bond, biphenyl, benzene or N-phenylcarbazole;
b represents: general formula (6), wherein Q is N, Q 1 And Q 2 Is phenyl; general formula (15), wherein each Z 3 Independently CH, Z at the point of attachment 3 Is a carbon atom; general formula (14), wherein each Z 3 Independently CH or N, Z at the point of attachment 3 Is a carbon atom; general formula (13), wherein A is a single bond, X 5 Is a single bond or an oxygen atom, a is 0 or 1, each Z 3 Independently CH, Z at the point of attachment 3 Is a carbon atom; or general formula (9) wherein each Z 3 Independently N or CH, Z at the point of attachment 3 Is a carbon atom, Ar 1 Is phenyl.
In one embodiment of the present invention, the first organic compound may be selected from compounds 1A to 84A, but is not limited thereto:
Figure GDA0003709648560000101
Figure GDA0003709648560000111
Figure GDA0003709648560000121
the compounds 1A to 84A can be synthesized by methods known to those skilled in the art, for example, the methods described in chinese patent application nos. 2016102620883, 201610599615X, 2016102592879, 201610689673.1, 2016102592972, 201610265142X, 2016102648253, 2016102652028, 2018103328302, 2018103312304, 2018105605225, 201810547204.5, and 201811160661.5.
As the first organic compound of the present invention, one or more of the above-described 2A, 3A, 5A, 7A, 9A, 10A, 12A, 17A, 21A, 26A, 30A, 31A, 39A, 43A, 47A, 56A, 62A, 63A, 69A, 71A, 72A, 66A, 79A, 81A, 82A, 67A, 45A, 49A, 35A, and 15A is preferably used, and more preferably one or more of the above-described 2A, 5A, 7A, 21A, 31A, 39A, 47A, 56A, 69A, 71A, and 72A is used.
In one embodiment of the present invention, the second organic compound may be selected from compounds 127B to 223B, but is not limited thereto:
Figure GDA0003709648560000122
Figure GDA0003709648560000131
Figure GDA0003709648560000141
Figure GDA0003709648560000151
the compounds 127B to 223B can be synthesized by methods known to those skilled in the art, for example, the methods described in patent applications No. 2018114483566, No. 201811158828.4, No. 2018111610926, No. 201811160661.5, No. 2017110718197, No. 2017110811069.
As the second organic compound of the present invention, one or more of the above 127B, 129B, 130B, 139B, 140B, 153B, 155B, 160B, 161B, 162B, 163B, 173B, 174B, 187B, 188B, 199B, 207B, 209B, 215B, 216B is preferably used, and one or more of the above 127B, 129B, 130B, 139B, 153B, 173B, 174B, 187B, 207B, 215B is more preferably used.
The weight ratio of the first organic compound to the second organic compound may vary depending on the electrical characteristics of the first organic compound and the second organic compound. In one embodiment of the invention, the weight ratio of the first organic compound to the second organic compound may be in the range of about 1:10 to about 10:1, for example, in the range of about 1:9 to about 9: 1. For example, the weight ratio of the first organic compound to the second organic compound may be in the range of about 2:8 to about 8:2, may be in the range of about 3:7 to about 7:3, or may be about 5:5, but is not limited thereto.
In addition, the guest material in the emission layer may include a phosphorescent or fluorescent material in order to improve fluorescent or phosphorescent characteristics. The phosphorescent material includes a phosphorescent material such as a metal complex of iridium, platinum, or the like. For example, a green phosphorescent material such as ir (ppy)3[ fac-tris (2-phenylpyridine) iridium ], a blue phosphorescent material such as FIrpic or FIr6, and a red phosphorescent material such as Btp2Ir (acac) can be used. For the fluorescent material, those generally used in the art can be used. In a preferred embodiment of the present invention, the guest material of the emission layer used is selected from one of the following EMD-1 to EMD-23, but it is not limited thereto:
Figure GDA0003709648560000152
Figure GDA0003709648560000161
the amount of the guest material in the emission layer may generally be in the range of about 0.01 to 15, preferably 1 to 10, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the host material (i.e., the total weight of the first organic compound and the second organic compound), but is not limited thereto.
The thickness of the emissive layer may be about
Figure GDA0003709648560000162
Or, for example, in the range of about
Figure GDA0003709648560000163
In the presence of a surfactant. When the thickness of the emission layer is within any of these ranges, the light emission characteristics of the emission layer may be improved without significantly increasing the driving voltage.
In the present invention, the electron transport region may include a hole blocking layer, an Electron Transport Layer (ETL), an electron injection layer, but is not limited thereto.
The electron transport region may include a hole blocking layer. When a phosphorescent material is included in the emission layer, a hole blocking layer may be included to prevent diffusion of triplet excitons or holes into the electron transport layer.
When the electron transport region includes a hole blocking layer, the hole blocking layer may be formed on the emission layer by a method such as vacuum deposition, spin coating, casting, an LB method, inkjet printing, laser printing, or LITI. When the hole blocking layer is formed by vacuum deposition or spin coating, the deposition conditions or coating conditions may be similar to those for forming the hole injection layer.
For example, the hole blocking layer may include at least one selected from BCP and Bphen, but is not limited thereto.
Figure GDA0003709648560000164
The hole blocking layer may have a thickness of about
Figure GDA0003709648560000165
Within the range of, for example, about
Figure GDA0003709648560000166
Within the range of (1). When the thickness of the hole blocking layer is in any of these ranges, the hole blocking property of the hole blocking layer can be improved without significantly increasing the driving voltage.
The electron transport region may further include an electron transport layer. The electron transport layer may be formed on the emission layer or on the charge control layer by a method such as vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, or laser induced thermal imaging. When the electron transport layer is formed by vacuum deposition or spin coating, the conditions for vacuum deposition and coating of the electron transport layer may be similar to those for vacuum deposition and coating of the hole injection layer.
The electron transport layer may include the above BCP and BPhen and the following Alq3, Balq, TAZ, NTAZ, and ET1 to ET 9:
Figure GDA0003709648560000171
the electron transport layer may have a thickness of about
Figure GDA0003709648560000172
Within the range of, for example, about
Figure GDA0003709648560000173
In the presence of a surfactant. When the thickness of the electron transport layer is within any of these ranges, the electron transport property of the electron transport layer can be improved without significantly increasing the driving voltage.
In addition, the electron transport layer may include a metal-containing material in addition to the above materials.
The metal-containing material may include a Li complex. Li complexes may include, for example, the compounds ET-D1 (lithium hydroxyquinoline, LiQ) or ET-D2:
Figure GDA0003709648560000174
it is particularly preferred that the electron transport layer comprises ET1/LiQ in a mass ratio of 1: 1.
The electron transport region may include an electron injection layer that may facilitate injection of electrons from the second electrode 190.
The electron injection layer may be formed on the electron transport layer by a method such as vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, LITI, or the like. When the electron injection layer is formed by vacuum deposition or spin coating, the conditions for vacuum deposition and coating of the electron injection layer may be similar to those for vacuum deposition and coating of the hole injection layer.
The electron injection layer can include, but is not limited to Yb, LiF, NaCl, CsF, Li 2 O, BaO and LiQ.
The electron injection layer may have a thickness of about
Figure GDA0003709648560000175
Within the range of, for example, about
Figure GDA0003709648560000176
Within the range of (1). When the thickness of the electron injection layer is within any of these ranges, the electron injection characteristics of the electron injection layer can be improved without significantly increasing the driving voltage.
The second electrode 190 may be positioned on the electron transport region. The second electrode 190 may be a cathode (i.e., an electron injection electrode). When the second electrode 190 is a cathode, a material for forming the second electrode 190 may be a material having a low work function, such as a metal, an alloy, a conductive compound, or a mixture thereof. Non-limiting examples of the second electrode 190 may include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), and aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) In a mass ratio ranging from 9:1 to 1: 9. In one embodiment of the present invention, the material for forming the second electrode 190 may be ITO or IZO. The thickness of the second electrode depends on the material used and is typically 5-100nm, preferably 7-30nm and more preferably 10-20 nm.
In order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer) can be added on the cathode of the device. According to the principle of optical absorption and refraction, the CPL cover layer material should have a higher refractive index as well as a better refractive index, and the absorption coefficient should be smaller as well. Any material known in the art may be used as the CPL layer material, such as Alq 3. The CPL capping layer is typically 5-300nm, preferably 20-100nm and more preferably 40-80nm thick.
The organic electroluminescent device may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layers of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.
The present invention also relates to a method of preparing an organic electroluminescent device comprising successively laminating a first electrode, an organic layer and a second electrode on a substrate. In this regard, vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, LITI, or the like may be used, but is not limited thereto. In the present invention, it is preferable to form the respective layers using a vacuum deposition method, wherein the deposition temperature of about 100-500 ℃ may be at about 10 DEG -8 -10 -3 Vacuum degree of tray and its combination
Figure GDA0003709648560000181
The deposition rate of (a) is vacuum deposition. Preferably, the deposition temperature is 200- -7 -10 -4 Tray, more preferably 10 -6 -10 -5 A deposition rate of about
Figure GDA0003709648560000182
More preferably about
Figure GDA0003709648560000183
The material for forming each layer according to the present invention may be used as a single layer by forming a film alone, may be used as a single layer by forming a film in admixture with another material, or may be used as a laminated structure of layers formed alone, layers formed in admixture with each other, or a laminated structure of layers formed alone and layers formed in admixture with each other.
The invention also relates to a display device, in particular a flat panel display device, comprising the organic electroluminescent device 10. The display device may further include at least one thin film transistor. The thin film transistor may include a gate electrode, source and drain electrodes, a gate insulating layer, and an active layer, wherein one of the source and drain electrodes may be electrically connected to the first electrode 110 of the organic electroluminescent device 10. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but is not limited thereto.
Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, characteristics and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics and/or elements described in connection with other embodiments, unless specifically indicated otherwise, as will be apparent to one of ordinary skill in the art upon submission of the present application. Accordingly, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.
Examples
Unless otherwise indicated, various materials used in the following examples and comparative examples are commercially available or may be obtained by methods known to those skilled in the art.
I. Preparation of the first organic Compound Material
1. Synthesis of Compound 2A
Figure GDA0003709648560000184
In a 500ml four-necked flask, 0.01mol of 2-bromooxaanthrone (raw material A1), 0.015mol of raw material B1, 0.03mol of sodium tert-butoxide, and 1X 10 mol of sodium tert-butoxide were added under a nitrogen gas atmosphere -4 mol tris (dibenzylideneacetone) dipalladium Pd 2 (dba) 3 、1×10 -4 mol tri-tert-butylphosphine P (t-Bu) 3 And 150ml of toluene, heating and refluxing for 24 hours, sampling, putting on a spot plate, completely reacting, naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain the target product with the purity of 99.26 percent and the yield of 57.62 percent.
Elemental analysis Structure (C) 53 H 37 NO 2 ) Theoretical value: c, 88.43; h, 5.18; n,1.95 test value: c, 88.47;h, 5.19; n, 1.93. Hrms (ei): theoretical value: 719.28, found: 719.23.
the following compounds (all starting materials were purchased from midrange energy-saving wanun co ltd) were prepared in the same or similar manner as compound 2A, and the synthetic starting materials and mass spectrometry data are shown in table 1 below;
TABLE 1
Figure GDA0003709648560000191
Figure GDA0003709648560000201
The synthesis of the above materials is referred to the patents (2016102620883, 201610599615X, 2016102592879, 201610689673.1, 2016102592972, 201610265142X, 2016102648253, 2016102652028, 2018103328302, 2018103312304, 2018105605225, 201810547204.5 and 201811160661.5) already applied by the applicant of the present invention.
Preparation of the second organic Compound
1. Synthesis of Compound 127B
Figure GDA0003709648560000202
In a 500ml four-necked flask, 0.01mol of the raw material C1 and 0.015mol of the raw material D2 were charged in a nitrogen-purged atmosphere, and dissolved in a mixed solvent of 180ml of toluene and 90ml of ethanol, and then 0.03mol of Na was added 2 CO 3 Aqueous solution (2M) and then 0.0001mol of tetrakis (triphenylphosphine) palladium Pd (PPh) was added 3 ) 4 Heating and refluxing for 10-24 h, sampling the sample, and completing the reaction. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 98.98% and the yield of 65.32%.
Elemental analysis Structure (C) 40 H 25 N 3 O 2 ) Theoretical value: c, 82.88; h, 4.35; n,7.25 test value: c, 82.86; h, 4.37; and N, 7.27. Hrms (ei): theoretical value: 579.19, found: 579.21。
The following compounds (all starting materials were purchased from midrange energy-saving wanun co ltd) were prepared in the same or similar manner as compound 127B, and the synthetic starting materials and mass spectrometry data are shown in table 2 below;
TABLE 2
Figure GDA0003709648560000211
Figure GDA0003709648560000221
The synthesis of the above materials is referred to the patents (2018114483566, 201811158828.4, 2018111610926, 201811160661.5, 2017110718197 and 2017110811069) already filed by the applicant of the present invention.
Preparation of organic electroluminescent device
The structural formula of the materials involved in the following preparation is as follows:
Figure GDA0003709648560000222
example 1
As an anode, will be respectively
Figure GDA0003709648560000223
Thickness of deposited ITO/Ag/ITO glass substrate was cut into dimensions of 50mm by 0.4 mm. The substrates were sonicated in isopropanol and pure water for 10 minutes each, rinsed with ozone for 10 minutes, and then mounted on a vacuum depositor.
Depositing compounds HT23 and NDP (HT23 and NDP in a mass ratio of 97:3) on the anode to form a film having a thickness of
Figure GDA0003709648560000224
On the hole injection layer, compound HT23 is deposited to a thickness of
Figure GDA0003709648560000225
On the hole transport layer, compound EB4 was deposited to form a thickness of
Figure GDA0003709648560000226
And then co-depositing a compound 2A (first organic compound), a compound 127B (second organic compound), and a compound EMD-13 (guest material) on the electron blocking layer in a weight ratio of 47:47:6 to form a film having a thickness of
Figure GDA0003709648560000231
The emission layer of (1).
Subsequently, compound ET3 and LiQ were co-deposited on the emissive layer at a weight ratio of 100:100 to form a light emitting diode having a structure with
Figure GDA0003709648560000232
The electron transport layer of (1), depositing Yb on the electron transport layer to form a thickness of about
Figure GDA0003709648560000233
Then co-depositing Mg and Ag on the electron injection layer at a weight ratio of 1:9 to form a thin film having a thickness of
Figure GDA0003709648560000234
And then depositing CP-1 on the cathode layer to form a cathode having a thickness of
Figure GDA0003709648560000235
A light extraction layer (i.e., a CPL capping layer) of thickness, thereby fabricating the organic electroluminescent device 1.
Example 2 to example 60
Organic electroluminescent devices 2 to 60 were produced in the same manner as in example 1, except that the emission layers of examples 2 to 60 were formed with the compounds shown in table 3.
Comparative example 1 to comparative example 24
Organic electroluminescent devices (see comparative examples 1 to 24 in table 4) were prepared in the same manner as in example 1, except that the emission layers of comparative example 1 to comparative example 11 were formed with the compounds shown in table 3.
TABLE 3
Figure GDA0003709648560000236
Figure GDA0003709648560000241
Figure GDA0003709648560000251
Test examples
The organic electroluminescent devices prepared in examples 1 to 60 and comparative examples 1 to 24 were evaluated for driving voltage, current density, luminance, color, efficiency and lifetime of emitted light using a CS-2000 spectroradiometer measuring unit (available from KONICA MINOLTA). When the current density is 10mA/cm 2 The luminance at the time is the initial luminance, and the T95 lifetime is defined as the time taken for the luminance of the organic electroluminescent device to decay to 95% of its initial luminance. The results are shown in table 4.
TABLE 4
Figure GDA0003709648560000252
Figure GDA0003709648560000261
Figure GDA0003709648560000271
Figure GDA0003709648560000281
As shown by the results shown in table 4, the organic electroluminescent devices 1 to 60 prepared using the host material of the present invention as the emission layer may have improved characteristics as a whole, in particular, reduced driving voltage, reduced power consumption, compared to the comparative organic electroluminescent devices 1 to 24 prepared using the host material of the related art or using only one host material as the emission layer; the efficiency is greatly improved; the service life of the organic electroluminescent device is greatly prolonged.
Finally, the above embodiments are only used to illustrate the technical solution of the present invention and are not limited. Modifications and equivalents of the technical solution of the present invention may be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention, and the modifications and equivalents should be covered by the claims of the present invention.

Claims (11)

1. An organic electroluminescent device is provided with a substrate, a first electrode, an organic layer and a second electrode from bottom to top in sequence, wherein the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode, the organic layer comprises an emitting layer,
wherein the emissive layer comprises a host material and a dopant material,
wherein the emission layer includes a first organic compound and a second organic compound,
characterized in that the first organic compound is a compound represented by the general formula (2):
Figure FDA0003709648550000011
wherein, X 1 Is an oxygen atom, C (C) 1-6 Alkyl radical) 2 Or C (phenyl) 2 ；
m represents 1;
each Z is independently represented by a nitrogen atom or C (R) 8 ) (ii) a Z at the attachment site is represented as a carbon atom;
R 8 is hydrogen atom, deuterium, methylTert-butyl, phenyl, naphthyl or pyridyl;
ar is phenylene, biphenylene, naphthylene, carbazolyl, phenyl-substituted carbazolyl, or dibenzofuranylene;
X 2 is a single bond, C (phenyl) 2 Or C (C) 1-6 Alkyl radical) 2 ；
Each Z 1 Independently represent a nitrogen atom or C (R) 9 ) (ii) a Z at the connection site 1 Represented as a carbon atom;
R 9 is hydrogen atom, deuterium, methyl, tert-butyl, phenyl, naphthyl or pyridyl;
r in the general formula (2) 3 Or R 4 A possible attachment site;
R 3 、R 4 is a hydrogen atom or a structure of the general formula (4) and R 3 、R 4 Not simultaneously represented as a hydrogen atom;
Figure FDA0003709648550000012
wherein formula (4) is connected to formula (2) by a bond-ring via the position marked by;
X 3 、X 4 each independently represents a single bond, an oxygen atom, C (C) 1-6 Alkyl radical) 2 N (phenyl) or N (biphenyl); and X 3 、X 4 Does not represent a single bond at the same time;
each Z 2 Independently represents CH; z at the point of attachment 2 Represents a carbon atom;
alternatively, the first organic compound is a compound of formula (1-1),
Figure FDA0003709648550000013
wherein R in formula (1-1) 3 Possible positions of the parallel ring connection with the rest;
(X) i is an oxygen atom, C (C) 1-6 Alkyl radical) 2 Or C (phenyl) 2 ；
Each Z is independently CH or C (C) 1-6 Alkyl); z at the attachment site is represented as a carbon atom;
ar is phenylene or a single bond;
X 2 is a single bond, C (phenyl) 2 Or C (C) 1-6 Alkyl radical) 2 Or are each
Figure FDA0003709648550000021
Wherein represents a site of attachment to the remainder of the structural formula;
each Z 1 Independently CH, wherein Z is at the point of attachment 1 Is a carbon atom;
R 3 is a hydrogen atom, N (phenyl) 2 Or a structure represented by the general formula (4),
Figure FDA0003709648550000022
x in the general formula (4) 3 Or X 4 Independently a single bond, C (C) 1-6 Alkyl radical) 2 N (phenyl) or N (biphenyl), wherein the general formula (4) is represented by the structural formula and two adjacent Z's marked with the structural formula (1-1) 1 Are connected in a ring-by-ring manner;
each Z 2 Independently is CH;
alternatively, the first organic compound is the following compound:
Figure FDA0003709648550000023
Figure FDA0003709648550000031
wherein the second organic compound is a compound described by the general formula (3):
Figure FDA0003709648550000032
wherein, X 2 ' represents a single bond or an oxygen atom;
n represents 0 or 1;
ar' represents a single bond, biphenyl, benzene, naphthalene, dibenzofuran or N-phenylcarbazole;
each Z' is independently represented by a nitrogen atom or C (R) 8 ') to a host; z' at the attachment site is represented as a carbon atom;
R 8 ' represents a hydrogen atom, deuterium, methyl, t-butyl, phenyl, naphthyl or pyridyl;
b represents a structure represented by general formula (6), general formula (9), general formula (13), general formula (14) or general formula (15);
Figure FDA0003709648550000033
wherein "-" in general formula (6), general formula (9), general formula (13), general formula (14) or general formula (15) represents a site to which Ar' in general formula (3) is attached;
A、X 5 each independently represents a single bond, an oxygen atom, C (R) 14 )(R 15 ) Or N (R) 16 )；
a represents 0 or 1;
each Z 3 Each independently represents a nitrogen atom or C (R) 17 ) (ii) a Z at the point of attachment 3 Represents a carbon atom;
q represents N atom or C-H, and at least one Q represents nitrogen atom;
Q 1 、Q 2 、Ar 1 each independently represents phenyl, naphthyl, pyridyl or biphenyl;
R 14 -R 16 each independently represents methyl or phenyl;
R 17 represented by hydrogen atom, deuterium, C 1-30 Alkyl, phenyl, naphthyl or pyridyl.
2. The organic electroluminescent device according to claim 1, wherein the first organic compound is a compound of formula (1-1),
Figure FDA0003709648550000041
wherein R in formula (1-1) 3 Possible positions of the parallel ring connection with the rest;
(X) i is an oxygen atom, C (methyl) 2 Or C (phenyl) 2 ；
Each Z is independently CH or C (t-butyl), wherein Z at the point of attachment is a carbon atom;
ar is phenylene or a single bond;
X 2 is a single bond, C (phenyl) 2 Or C (methyl) 2 Or is or
Figure FDA0003709648550000042
Wherein represents a site of attachment to the remainder of the structural formula;
each Z 1 Independently CH, wherein Z is at the point of attachment 1 Is a carbon atom;
R 3 is a hydrogen atom, N (phenyl) 2 Or a structure of the general formula (4) in which X is 3 Or X 4 Independently a single bond, C (methyl) 2 N (phenyl) or N (biphenyl), wherein the general formula (4) is represented by the structural formula and two adjacent Z's marked with the structural formula (1-1) 1 Are connected in a ring-by-ring manner;
each Z 2 Independently CH.
3. The organic electroluminescent device according to claim 1, wherein the second organic compound is a compound represented by general formula (3), wherein
Each Z' is independently CH, C (phenyl), or C (t-butyl), wherein Z at the point of attachment is a carbon atom;
X 2 ' is an oxygen atom or a single bond;
n is 0 or 1;
ar' is a single bond, biphenyl, benzene or N-phenylcarbazole;
b is selected from: general formula (6), wherein Q is N, Q 1 And Q 2 Is phenyl; general formula (15), wherein each Z 3 Independently CH, Z at the point of attachment 3 Is a carbon atom; general formula (14), wherein each Z 3 Independently CH or N, Z at the point of attachment 3 Is a carbon atom; general formula (13), wherein A is a single bond, X 5 Is a single bond or an oxygen atom, a is 0 or 1, each Z 3 Independently CH, Z at the point of attachment 3 Is a carbon atom; or general formula (9) wherein each Z 3 Independently N or CH, Z at the point of attachment 3 Is a carbon atom, Ar 1 Is phenyl.
4. The organic electroluminescent device according to claim 1, wherein the first organic compound is selected from at least one of the following compounds:
Figure FDA0003709648550000043
Figure FDA0003709648550000051
Figure FDA0003709648550000061
5. the organic electroluminescent device according to claim 1, wherein the second organic compound is selected from at least one of the following compounds:
Figure FDA0003709648550000062
Figure FDA0003709648550000071
Figure FDA0003709648550000081
6. the organic electroluminescent device according to claim 1, wherein the weight ratio of the first organic compound to the second organic compound is in the range of 1:10 to 10: 1.
7. The organic electroluminescent device of claim 1, wherein the emissive layer further comprises a fluorescent or phosphorescent guest material.
8. The organic electroluminescent device of claim 7, wherein the amount of the fluorescent or phosphorescent guest material is in the range of 0.01 to 15, based on 100 parts by weight of the total weight of the first organic compound and the second organic compound.
9. The organic electroluminescent device according to claim 1, wherein when the first electrode is an anode and the second electrode is a cathode, the organic layer comprises a hole transport region between the first electrode and the emissive layer, and an electron transport region between the emissive layer and the second electrode,
the hole transport region sequentially comprises one or more combinations of a hole injection layer, a hole transport layer, a buffer layer and an electron blocking layer from bottom to top; the electron transport region comprises one or more combinations of a hole blocking layer, an electron transport layer and an electron injection layer from bottom to top in sequence.
10. A method of producing the organic electroluminescent device as claimed in any one of claims 1 to 9, comprising successively laminating a first electrode, an organic layer and a second electrode on a substrate,
the lamination is carried out by means of vacuum deposition at a deposition temperature of 100-500 DEG CAt the degree of 10 -8 -10 -3 Vacuum degree of tray and
Figure FDA0003709648550000082
the deposition rate of (3).
11. A display apparatus comprising the organic electroluminescent device according to any one of claims 1 to 9.
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CN107068910A (en) * 2016-04-25 2017-08-18 中节能万润股份有限公司 A kind of organic electroluminescence device of compound containing xanthone and its application
CN107245079A (en) * 2016-12-30 2017-10-13 江苏三月光电科技有限公司 A kind of azepine xanthone compound and its application in OLED
CN107275496A (en) * 2016-04-07 2017-10-20 三星显示有限公司 Organic luminescent device

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Publication number Priority date Publication date Assignee Title
CN107275496A (en) * 2016-04-07 2017-10-20 三星显示有限公司 Organic luminescent device
CN107068910A (en) * 2016-04-25 2017-08-18 中节能万润股份有限公司 A kind of organic electroluminescence device of compound containing xanthone and its application
CN107245079A (en) * 2016-12-30 2017-10-13 江苏三月光电科技有限公司 A kind of azepine xanthone compound and its application in OLED

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