CN113594375B - Green light organic electroluminescent device - Google Patents
Green light organic electroluminescent device Download PDFInfo
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- CN113594375B CN113594375B CN202010360764.7A CN202010360764A CN113594375B CN 113594375 B CN113594375 B CN 113594375B CN 202010360764 A CN202010360764 A CN 202010360764A CN 113594375 B CN113594375 B CN 113594375B
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- 239000000463 material Substances 0.000 claims abstract description 167
- -1 naphthalene anthracene compound Chemical class 0.000 claims abstract description 31
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- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 53
- 125000000217 alkyl group Chemical group 0.000 claims description 41
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- 229910052805 deuterium Inorganic materials 0.000 claims description 29
- 229910052722 tritium Inorganic materials 0.000 claims description 29
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
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- 238000000034 method Methods 0.000 claims description 24
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- 229910052744 lithium Inorganic materials 0.000 description 1
- GUWHRJQTTVADPB-UHFFFAOYSA-N lithium azide Chemical compound [Li+].[N-]=[N+]=[N-] GUWHRJQTTVADPB-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 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
- 239000008204 material by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UVEAFTFQMHUWEY-UHFFFAOYSA-N methane;1,2,4,5-tetrafluoro-3,6-dioxocyclohexane-1,2,4,5-tetracarbonitrile Chemical compound C.C.N#CC1(F)C(=O)C(F)(C#N)C(F)(C#N)C(=O)C1(F)C#N UVEAFTFQMHUWEY-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000004059 quinone derivatives Chemical class 0.000 description 1
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a green organic electroluminescent device, comprising: the organic light-emitting diode comprises a substrate layer, a first electrode, an organic light-emitting functional layer, a second electrode and a covering layer, wherein the organic light-emitting functional layer comprises a main body material and a doping material, the main body material is a naphthalene anthracene compound, and the doping material is selected from boron compounds. The invention can greatly improve the luminous efficiency of the device and the stability of the device due to the strong TTA effect of the device and the bipolar and asymmetric characteristics of the boron material.
Description
Technical Field
The invention relates to the technical field of semiconductors. In particular, the invention relates to a green light organic electroluminescent device with a luminescent layer host and guest matched.
Background
The organic electroluminescent (OLED: organic Light Emitting Diodes) device technology can be used for manufacturing novel display products and novel illumination products, is hopeful to replace the existing liquid crystal display and fluorescent lamp illumination, and has wide application prospect. In general, an organic electroluminescent device composed of several layers includes an anode, a cathode, a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied to electrodes at both ends of the organic electroluminescent device, holes from the anode and electrons from the cathode are recombined in the organic luminescent layer by an electric field to form excitons, and the excitons relax to a ground state to release energy, thereby generating organic electroluminescence.
The current performance research of organic electroluminescent devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, prolonging the service life of the device, and the like. In order to realize the continuous improvement of the performance of the organic electroluminescent device, not only the innovation of the structure and the preparation process of the organic electroluminescent device, but also the continuous research and innovation of the organic electroluminescent functional material are needed to manufacture the organic electroluminescent device with higher performance.
In an OLED light emitting device, positive charges are injected from the anode, negative charges are injected from the cathode, and negative and positive charge carriers recombine at the light emitting layer of the device and form two excited states: intermolecular negative-positive charge pairs (polaron pairs) and intramolecular negative-positive charge pairs (excitons). Based on the principle of spin statistics, these excited states are in turn divided into singlet and triplet states. The singlet excitons generate instant fluorescence luminescence through radiation transition, while the radiation recombination of the triplet excitons is spin forbidden and cannot directly participate in luminescence, but can be mutually coupled under certain conditions to generate singlet excitons, thereby forming delayed electroluminescence, namely delayed luminescence, also called TTF coupled luminescence. In theory, the internal quantum efficiency of the TTF fluorescent device can reach 62.5%, which is far higher than that of the traditional fluorescent light by 25%, and the TTF fluorescent device has an important effect on improving the efficiency of the OLED luminescent device.
Based on fluorescent host and guest material collocation devices, the necessary conditions for generating stable and efficient TTF coupling luminescence include:
1) Energy transfer between host material and dopant materialEnergy transfer rules.
2) The energy of the singlet excitons of the host material is similar to twice the energy of the triplet excitons.
3) The main guest material has proper energy level collocation.
4) Efficient injection of positive and negative charges into the light-emitting layer and good carrier balance.
Therefore, according to the current industrial application requirements of the OLED device and the requirements of different functional film layers of the OLED device, the photoelectric characteristic requirements of the device are required to select more suitable OLED functional materials or material combinations with higher performance so as to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. For the TTF-characteristic OLED light emitting device, in order to pursue stable and efficient TTF light emitting effect, there is a certain requirement on physical properties of host and guest materials, and at the same time, it is required that the host and guest materials have an optimal combination and collocation form, and that the light emitting layer has good injection and transmission and good carrier balance.
Disclosure of Invention
In order to solve the above problems, the present invention aims to find a suitable host material with TTF effect and boron-containing doping material to obtain a green organic electroluminescent device with high efficiency and high stability.
The invention provides an organic electroluminescent device, which sequentially comprises a substrate, a first electrode, an organic functional material layer and a second electrode from bottom to top, wherein the organic functional material layer comprises:
a hole transport region located over the first electrode;
a light emitting layer over the hole transport region, the light emitting layer comprising a host material and a dopant material;
an electron transport region located over the light emitting layer;
and a cover layer over the second electrode;
wherein the light-emitting layer comprises a host material represented by the following general formula (1) and a doping material represented by the general formula (2);
wherein the host material is an anthracene compound having a general formula (1),
Z、Z 1 and Z 2 Each occurrence of which is independently represented by N or C-R, which may be the same or different, R is independently represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the doping material is selected from one of the general formula (2):
wherein,
In the general formula (2), W 1 、W 2 、W 3 Each independently of the other is represented by a nitrogen atom or a boron atom, and W 1 、W 2 、W 3 Wherein only one of the two is represented by a nitrogen atom;
a. b, c, d, e are each independently represented as 0 or 1, and a+b+c+d+e is not less than 1;
X 1 、X 2 、X 3 、X 4 、X 5 independently represents a single bond, a sulfur atom, an oxygen atom,N(R 6 )、B(R 7 )、C(R 8 )(R 9 ) Or Si (R) 10 )(R 11 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 8 And R is R 9 、R 10 And R is R 11 Can be connected with each other to form a ring;
X 1 、X 2 、X 3 、X 4 、X 5 at least one of which is not represented by a single bond;
α, β, γ, η, θ are each independently represented as 1, 2 or 3;
Y 1 to Y 21 Each independently represents a carbon atom, a nitrogen atom or C-R;
r is hydrogen atom, protium, deuterium, tritium, cyano, halogen atom, C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 6 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups;
l is independently represented by a single bond, C 6 -C 30 Arylene, substituted or unsubstituted C 3 -C 30 Is a heteroarylene group;
R 1 to R 5 Each independently represents a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, or C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 5 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups; r1 to R5 are connected with the general formula (1) in a ring combining and substitution mode, and asterisks in the general formula (1) indicate connectable sites;
The R is 6 -R 11 Respectively and independently denoted as C 1 -C 20 Alkyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2); r6, R7 may be linked to an adjacent group and form a ring structure;
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium, cyano, fluorine atom, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
The core of the invention is to provide a selection mode of a host material and a doping material for preparing a high-performance organic electroluminescent device. Based on the selection mode provided by the invention, the high-performance green light organic electroluminescent device can be prepared by adopting the main material and the doping material.
Compared with the prior art, the invention has the beneficial effects that:
the naphthyl anthracene is used as a main body material of a core, and can form a stable dimer structure due to a larger conjugated structure. Meanwhile, the included angle between the naphthyl and the anthracene is just to enable the center distance of every two molecules to be kept at a stable safe distance, repulsive force can not be generated, and certain electronic cloud overlapping exists. This interaction gives the material a better TTA effect. In addition, the HOMO and LUMO distribution of the material are mainly distributed on anthracene, and when carriers are transmitted on the material, intermolecular transmission is easier, so that the starting voltage and the driving voltage of the device can be effectively reduced.
The main material taking the naphthyl anthracene as the core has a strong TTA effect, and the efficiency of the device can be effectively improved by matching with the green light doping material taking boron as the framework. In addition, the boron group is a bipolar group, the whole molecular structure is an asymmetric group, the symmetry of the molecular structure is destroyed, the aggregation among molecules is avoided, and the reduction of the stability of the material caused by higher local energy is prevented.
Therefore, the organic electroluminescent device manufactured by the method can effectively reduce the voltage of the device and improve the efficiency and stability of the device.
Drawings
Fig. 1 schematically shows a cross-sectional view of an organic electroluminescent device of the present invention.
In fig. 1, 1. A substrate; 2. a first electrode; 3. a hole injection layer; 4. a hole transport layer; 5. an electron blocking layer; 6. a light emitting layer; 7. a hole blocking layer; 8. an electron transport layer; 9. an electron injection layer; 10. a second electrode; 11. a cover layer; A. an electron transport region; B. hole transport regions.
Detailed Description
The invention will be described in more detail hereinafter with reference to the accompanying drawings, but is not intended to limit the invention.
In the present invention, unless otherwise indicated, all operations are carried out at room temperature under normal pressure.
In the present invention, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule unless otherwise specified. Further, reference in the present specification to "difference in HOMO energy levels" and "difference in LUMO energy levels" means a difference in absolute values of each energy value. Furthermore, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between energy levels is also a comparison of the magnitudes of the absolute values thereof, and those skilled in the art know that the larger the absolute value of an energy level, the lower the energy of the energy level.
Any numerical range recited herein is intended to include all sub-ranges subsumed therein with the same numerical accuracy. For example, "1.0 to 10.0" means all subranges included between the minimum value of 1.0 listed and the maximum value of 10.0 listed (and including 1.0 and 10.0), that is, all subranges having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0. Any maximum numerical limitation listed herein is meant to include all smaller numerical limitations, and any minimum numerical limitation listed herein is meant to include all larger numerical limitations, all smaller numerical limitations, and all smaller numerical limitations, all larger numerical limitations, and all smaller numerical limitations, all as recited herein are meant to be included herein. Accordingly, the applicant reserves the right to modify the present specification including the claims to expressly describe any subranges falling within the scope of the explicit description herein.
In the drawings, the size of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. Further, it will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers or one or more intervening layers may also be present. Like numbers refer to like elements throughout.
In the present invention, when describing electrodes and organic electroluminescent devices, as well as other structures, words of "upper", "lower", "top" and "bottom", etc., which are used to indicate orientations, indicate only orientations in a certain specific state, and do not mean that the relevant structure can only exist in the orientations; conversely, if the structure can be repositioned, for example inverted, the orientation of the structure is changed accordingly. Specifically, in the present invention, the "bottom" side of an electrode refers to the side of the electrode that is closer to the substrate during fabrication, while the opposite side that is farther from the substrate is the "top" side.
The invention provides an organic electroluminescent device, which sequentially comprises a substrate, a first electrode, an organic functional material layer and a second electrode from bottom to top, wherein the organic functional material layer comprises:
A hole transport region located over the first electrode;
a light emitting layer over the hole transport region, the light emitting layer comprising a host material and a dopant material;
an electron transport region located over the light emitting layer;
and a cover layer over the second electrode;
wherein the light-emitting layer comprises a host material represented by the following general formula (1) and a doping material represented by the general formula (2);
wherein the host material is an anthracene compound having a general formula (1),
Z、Z 1 and Z 2 Each occurrence of which is independently represented by N or C-R, which may be the same or different, R is independently represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the doping material is selected from one of the general formula (2):
in the general formula (2), W 1 、W 2 、W 3 Each independently of the other is represented by a nitrogen atom or a boron atom, and W 1 、W 2 、W 3 Wherein only one of the two is represented by a nitrogen atom;
a. b, c, d, e are each independently represented as 0 or 1, and a+b+c+d+e is not less than 1;
X 1 、X 2 、X 3 、X 4 、X 5 Independently represents a single bond, a sulfur atom, an oxygen atom,N(R 6 )、B(R 7 )、C(R 8 )(R 9 ) Or Si (R) 10 )(R 11 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 8 And R is R 9 、R 10 And R is R 11 Can be connected with each other to form a ring;
X 1 、X 2 、X 3 、X 4 、X 5 at least one of which is not represented by a single bond;
α, β, γ, η, θ are each independently represented as 1, 2 or 3;
Y 1 to Y 21 Each independently represents a carbon atom, a nitrogen atom or C-R;
r is hydrogen atom, protium, deuterium, tritium, cyano, halogen atom, C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 6 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups;
l is independently represented by a single bond, C 6 -C 30 Arylene, substituted or unsubstituted C 3 -C 30 Is a heteroarylene group;
R 1 to R 5 Each independently represents a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, or C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 5 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups; r1 to R5 are connected with the general formula (1) in a ring combining and substitution mode, and asterisks in the general formula (1) indicate connectable sites;
the R is 6 -R 11 Respectively and independently denoted as C 1 -C 20 Alkyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2); r is R 6 、R 7 Can be linked to an adjacent group and form a ring structure;
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium, cyano, fluorine atom, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
Further, when a, b, c, d, e are each independently represented as 0, Y 1 To Y 21 Each independently of the others is represented by a nitrogen atom or C-R or C-L-R 1 Or C-L-R 2 Or C-L-R 3 Or C-L-R 4 Or C-L-R 5 The method comprises the steps of carrying out a first treatment on the surface of the When a, b, c, d, e are each independently represented as 1, Y 21 、Y 1 ，Y 16 、Y 17 、Y 13 、Y 14 、Y 8 、Y 9 、Y 4 、Y 5 Represented by carbon atoms only, the remainder being independently of one another represented by nitrogen atoms or C-R or C-L-R 1 Or C-L-R 2 Or C-L-R 3 Or C-L-R 4 Or C-L-R 5 ；
R is hydrogen atom, protium, deuterium, tritium, cyano, halogen atom, C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 6 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups;
R 1 to R 5 Each independently represents a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, or C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 5 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups; r1 to R5 are connected with the general formula (1) in a ring combining and substitution mode, and asterisks in the general formula (1) indicate connectable sites.
Further, the L's are the same or different and represent a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted spirofluorenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenyl group.
Further, R 1 To R 5 Each independently represents a structure represented by the general formula (a) and the general formula (b);
in the general formula (a) and the general formula (b), R is 12 、R 13 Each independently represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted azabenzophenanthryl group, a substituted or unsubstituted azacarbazolyl group, a substituted or unsubstituted benzocarbazolyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted naphthyridinyl group, a group represented by the general formula (4), the general formula (5) or the general formula (6); r is R 12 、R 13 The same or different; s, t represent 0 or 1;
X 6 、X 9 represented by oxygen atom, sulfur atom, -N (R) 14 )-、-C(R 15 )(R 16 ) -or-Si (R) 17 )(R 18 )-；
X 7 、X 8 Independently of each other, can also be represented by a single bond, an oxygen atom, a sulfur atom, -N (R) 14 )-、-C(R 15 )(R 16 ) -or-Si (R) 17 )(R 18 )-；
Z is identically or differently denoted for each occurrence as N atom or C-R 19 ；
The R is 14 -R 18 Respectively and independently denoted as C 1 -C 20 Alkyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2);
the R is 19 Identically or differently selected from hydrogen atoms, protium atoms, deuterium atoms, tritium atoms, fluorine atoms, cyano groups, C 1 -C 20 Alkyl, C of (2) 2 -C 20 Is an olefinic group, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 One of the 5-30 heteroaryl groups of (a); wherein two or more R 19 The groups are linked to each other and form a ring or are not cyclic;
the general formula (4) and the general formula (5) are fused and connected with two adjacent positions marked in the general formula (2) or the general formula (3) through two adjacent positions marked in the x;
Ar 1 、Ar 2 each independently represents substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2);
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium, cyano, fluorine atom, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
The heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
The doping material may be further represented by the following general formula (3):
in the general formula (3), W 1 、W 2 、W 3 Each independently of the other is represented by a nitrogen atom or a boron atom, and W 1 、W 2 、W 3 Wherein only one of the two is represented by a nitrogen atom;
b. c, d, e are each independently 0 or 1, and a+b+c+d+e is not less than 1;
X 1 、X 2 、X 3 、X 4 、X 5 independently represents a single bond, a sulfur atom, an oxygen atom,N(R 6 )、B(R 7 )、C(R 8 )(R 9 ) Or Si (R) 10 )(R 11 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 8 And R is R 9 、R 10 And R is R 11 Can be connected with each other to form a ring;
X 1 、X 2 、X 3 、X 4 、X 5 at least one of which is not represented by a single bond;
α, β, γ, η, θ are each independently represented as 1, 2 or 3;
when a, b, c, d, e are respectively and independently represented as 0, Y 1 To Y 21 Each independently represents a nitrogen atom or CH; when a, b, c, d, e are each independently represented as 1, Y 21 、Y 1 ，Y 16 、Y 17 、Y 13 、Y 14 、Y 8 、Y 9 、Y 4 、Y 5 Represented as a carbon atom, the remainder may each independently represent a nitrogen atom or CH;
R 1 to R 5 Each independently represents a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, or C 1 -C 20 Alkyl, C 1 -C 20 Alkyl substituted silanesRadicals, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups; r is R 1 To R 5 The connection mode with the general formula (1) comprises two modes of ring combination and substitution;
the R is 6 -R 11 Respectively and independently denoted as C 1 -C 20 Alkyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2); r is R 6 、R 7 Can be linked to an adjacent group and form a ring structure;
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium, cyano, fluorine atom, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatom is any one or more selected from oxygen, sulfur or nitrogen atoms.
Further, when said R 1 To R 5 When connected with the general formula (1) in a substituted manner, the compounds are respectively and independently represented by a hydrogen atom, protium, deuterium, tritium, cyano, fluorine atom, methyl, ethyl, propyl, butyl, tertiary butyl, amyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted azacarbazolyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted pyrenyl or the structure shown in the general formula (2); when said R is 1 To R 5 When connected with the general formula (1) in a parallel ring mode, the two are respectively and independently represented as one of structures shown in the general formula (3) or the general formula (4);
the L is 1 Represented by a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted spirofluorenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenyl group;
Ar 1 、Ar 2 each independently represents substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2);
X 6 、X 7 represented by oxygen atom, sulfur atom, -N (R) 12 )-、-C(R 13 )(R 14 ) -or-Si (R) 15 )(R 16 ) -; wherein X is 6 May also be denoted as single bond;
Z 1 to Z 4 Each independently of the other is represented by a nitrogen atom or C-R 17 ；
The R is 12 -R 16 Respectively and independently denoted as C 1 -C 20 Alkyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2);
the R is 17 Identically or differently selected from hydrogen atoms, protium atoms, deuterium atoms, tritium atoms, fluorine atoms, cyano groups, C 1 -C 20 Alkyl, C of (2) 2 -C 20 Is an olefinic group, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2); wherein two or more R 9 The groups may be linked to each other and may form a ring structure;
the general formula (3) or the general formula (4) is connected with the general formula (1) in a parallel ring mode, wherein the general formula is expressed as a connecting site, and when the ring is used, only two adjacent sites can be taken;
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium, cyano, fluorine atom, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
Further, the C 6-30 Arylene of (a) is represented by phenylene, naphthylene, and biphenylene;
the C is 3-30 Heteroarylene is represented by one of a pyridyl group, a carbazolyl group, a furanyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a dibenzofuranyl group, a 9, 9-dimethylfluorenyl group, an N-phenylcarbazolyl group, a quinolinyl group, an isoquinolinyl group, and a naphthyridinyl group;
the C is 1-20 The alkyl is one of methyl, ethyl, propyl, isopropyl, tertiary butyl, butyl and amyl;
the C is 6-30 Aryl of (2) is one of phenyl, fluorenyl, spirofluorenyl, naphthyl, biphenyl, terphenyl, anthryl, phenanthryl, pyrenyl and benzophenanthryl;
The C is 3-30 Heteroaryl is represented by one of pyridyl, carbazolyl, furyl, pyrimidinyl, pyrazinyl, pyridazinyl, thienyl, dibenzofuranyl, 9-dimethylfluorenyl, N-phenylcarbazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, oxazolyl, imidazolyl, benzoxazolyl, benzimidazolyl, azacarbazolyl, and benzocarbazolyl.
The host material may be represented by one of the following general formulas (4) to (6),
in the general formulae (4) to (6),
Z、Z 1 and Z 2 Each occurrence of which is independently represented by N or C-R, which may be the same or different, R is independently represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium and C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
The first compound in the fluorescent light-emitting layer may be represented by one of the following general formulas (7) to (9),
R 1 ～R 14 And Ra, rb are each independently represented as a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium and C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
The host material may be represented by one of the following general formulas (10) to (12),
R 1 ～R 14 and Ra, rb are each independently represented as a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the substituents of the substitutable groups are optionally selected from protium, deuterium, tritium and C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
Further, the X is 1 、X 2 、X 3 、X 4 、X 5 At least one of which is represented as N (R 6 )。
Further, the X is 1 、X 2 、X 3 、X 4 、X 5 At least two of which are represented as N (R 6 )。
The host material may be selected from the following structural features:
the doping material may be selected from the following structural features:
the organic functional layer of the organic electroluminescent device comprises a P-type material doped hole transport layer, a hole transport layer, an electron blocking layer, a fluorescent light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.
The doping material accounts for 1-10% of the mass fraction of the main body material, and is preferably located at 2-5%.
The high-performance OLED light-emitting device is provided with good carrier conduction characteristics and good carrier balance in the light-emitting layer composite region. In order to obtain good carrier balance, excellent injection and conduction characteristics of holes and electrons are indispensable.
The naphthyl anthracene is used as a main body material of a core, and can form a stable dimer structure due to a larger conjugated structure. Meanwhile, the included angle between the naphthyl and the anthracene is just to enable the center distance of every two molecules to be kept at a stable safe distance, repulsive force can not be generated, and certain electronic cloud overlapping exists. This interaction gives the material a better TTA effect. In addition, the HOMO and LUMO distribution of the material are mainly distributed on anthracene, and when carriers are transmitted on the material, intermolecular transmission is easier, so that the starting voltage and the driving voltage of the device can be effectively reduced.
Because the main material taking the naphthalene anthracene as the core has a strong TTA effect, the efficiency of the device can be effectively improved by matching with the doping material taking boron as the framework. In addition, the boron group is a bipolar group, and the molecular structure is a non-stacked structure, so that the symmetry of the molecular structure is broken, the aggregation among molecules is avoided, and the reduction of the stability of the material due to higher local energy is prevented.
Therefore, the host and guest collocation in the invention can effectively improve the efficiency of the device due to the strong TTA effect of the host material, and can effectively improve the stability of the device due to the bipolar group and long chain structure of the boron group on the other hand.
As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used for organic electroluminescent devices may be used. Examples are transparent substrates, such as glass or transparent plastic substrates; an opaque substrate such as a silicon substrate; a flexible PI film substrate. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, and water repellency. The use direction of the substrate is different according to the property of the substrate. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.
A first electrode is formed on the substrate, and the first electrode and the second electrode may be opposite to each other. The first electrode may be an anode. The first electrode is a reflective electrode, which may comprise Ag, mg, al, pt, pd, au, ni, nd, ir, cr or a metal mixture. The thickness of the first electrode layer depends on the material used, and is typically 50 to 500nm, preferably 70 to 300nm and more preferably 100 to 200nm.
The organic functional material layer arranged between the first electrode and the second electrode sequentially comprises a hole transmission region, a light emitting layer and an electron transmission region from bottom to top.
The hole transport region may be disposed between the first electrode and the light emitting layer. The hole transport region may include a hole injection layer, a hole transport layer, and an electron blocking layer. For example, referring to fig. 1, the hole transport region may include a hole injection layer, a hole transport layer, and an electron blocking layer sequentially disposed over the first electrode from bottom to top.
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 multilayer structure having a plurality of layers formed of a plurality of different materials.
When the hole transport region includes a hole injection layer, the material of the hole injection layer is preferably a material having a high work function so that holes are easily injected into the organic functional 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-toluene-amino) -phenyl ] -biphenyl-4, 4 '-diamine (DNTPD), 4',4 "-tris (3-methylphenyl-phenylamino) triphenylamine (m-MTDATA), 4',4" -tris (N, N-diphenylamino) triphenylamine (TDATA), 4',4 "-tris { N, - (2-naphthyl) -N-phenylamino } -triphenylamine (2 TNATA), 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/P-1 (specific structural formulae will be shown below). The thickness of the hole injection layer of the present invention may be 1 to 100nm, preferably 2 to 50nm and more preferably 5 to 20nm.
When the hole transport region includes a hole transport layer, the material of the hole transport layer is preferably a material having high hole mobility, which enables holes to be transferred from the anode or the hole injection layer to the light emitting layer. The hole transport material may include the following compounds HT1 to HT25, but is not limited thereto:
according to the present invention, HT23 is preferably used 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 180nm, and more preferably 20 to 150nm.
In addition to the above materials, the hole injection layer and/or the hole transport layer may further include a charge generation material to improve conductive properties. The charge generating material may be uniformly or non-uniformly dispersed in the hole injection layer and/or the hole transport layer. The charge generating material may be, for example, a P-dopant. The P-dopant may be selected from 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-benzoquinone dimethane (F4-TCNQ); metal oxides such as tungsten oxide or molybdenum oxide; or cyano-containing compounds, such as compounds P1, NDP and F4-TCNQ shown below:
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 light emitting 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 specific embodiments, the electron blocking layer compound may be selected from the following compounds EB1 to EB7, but is not limited thereto:
The thickness of the electron blocking layer of the present invention may be 1 to 200nm, preferably 5 to 150nm and more preferably 10 to 100nm.
According to the present invention, a light emitting layer may be provided over the hole transport region. The material of the light emitting layer is a material capable of emitting visible light by receiving holes from the hole transporting region and electrons from the electron transporting region, respectively, and combining the received holes and electrons. The light emitting layer may include a host material and a dopant material.
In one embodiment of the present invention, the host material of formula (1) is selected from at least one of the following formulas: formula (BH 1), formula (BH 10), formula (BH 12), formula (BH 13), formula (BH 26), formula (BH 36), formula (BH 47), formula (BH 64), and formula (BH 67).
In one embodiment of the present invention, among the doping materials, the doping materials of the general formula (2) and the general formula (3) are selected from at least one of the following formulas: formula (DP-68), formula (DP-72), formula (DP-76), formula (DP-77), formula (DP-97), formula (DP-120), formula (DP-146), formula (DP-167), and formula (DP-180).
The compounds of the present invention may be commercially purchased from general energy saving Co., ltd, or may be prepared by the method described in the reference to the known patents CN110407858A, WO2019052940A1, CN107851724A, WO2019239897A1, CA3017010A1, CN110581224A, CN110612304A, CN107735879B, CN 109671852A.
In the light-emitting layer of the present invention, the ratio of host material to guest material used is 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13 on a mass basis.
The thickness of the light emitting layer may be adjusted to optimize light emitting efficiency and driving voltage. The preferred thickness range is 5nm to 50nm, but the thickness is not limited to this range.
In the present invention, the electron transport region may include a hole blocking layer, an electron transport layer, and an electron injection layer disposed over the light emitting layer in this order from bottom to top, but is not limited thereto.
The hole blocking layer is a layer that blocks holes injected from the anode from passing through the light emitting layer to the cathode, thereby extending the lifetime of the device and improving the efficiency of the device. The hole blocking layer of the present invention may be disposed over the light emitting layer. As the hole blocking layer material of the organic electroluminescent device of the present invention, compounds having a hole blocking effect known in the prior art, for example, phenanthroline derivatives such as bathocuproine (referred to as BCP), metal complexes of hydroxyquinoline derivatives such as aluminum (III) bis (2-methyl-8-quinoline) -4-phenylphenol (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, 9'- (5- (6- ([ 1,1' -biphenyl ] -4-yl) -2-phenylpyrimidin-4-yl) -1, 3-phenylene) bis (9H-carbazole) (CAS No. 1345338-69-3), and pyrimidine derivatives such as the like can be used. The hole blocking layer of the present invention may have a thickness of 2 to 200nm, preferably 5 to 150nm, and more preferably 10 to 100nm, but the thickness is not limited to this range.
The electron transport layer may be disposed over the light emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons of the cathode and transfers the received electrons to the light emitting layer. Materials with high electron mobility are preferred. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials for organic electroluminescent devices known in the art, for example, alq 3 Metal complexes of hydroxyquinoline derivatives represented by BAlq and Liq, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2, 4-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6- (naphthalen-2-yl) -1,3, 5-triazine (CAS No.: 1459162-51-6), and 2- (4- (9, 10-bis (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ]]Imidazole derivatives such as imidazole (CAS number: 561064-11-7, commonly known as LG 201), oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, and the like. The thickness of the electron transport layer of the present invention may be 10 to 80nm, preferably 20 to 60nm and more preferably 25 to 45nm, but the thickness is not limited to this range.
The electron injection layer may be disposed over the electron transport layer. The electron injection layer material is generally a material preferably having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, electron injection layer materials for organic electroluminescent devices known in the art, for example, lithium; lithium salts such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1 to 5nm, preferably 0.5 to 3nm, and more preferably 0.8 to 1.5nm, but the thickness is not limited to this range.
The second electrode may be disposed over the electron transport region. The second electrode may be a cathode. The second electrode may be a transmissive electrode, a semi-transmissive electrode or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode may comprise, for example, li, yb, ca, liF/Ca, liF/Al, al, mg, baF, ba, ag, or a compound or mixture thereof; when the second electrode is a semi-transmissive electrode or a reflective electrode, the second electrode may comprise Ag, mg, yb, al, pt, pd, au, ni, nd, ir, cr, li, ca, liF/Ca, liF/Al, mo, ti, or a compound or mixture thereof.
In the process of manufacturing the organic electroluminescent device, the organic electroluminescent device of the present invention may be manufactured, for example, by sequentially laminating a first electrode, an organic functional material layer, and a second electrode on a substrate. In this regard, a physical vapor deposition method such as a sputtering method or an electron beam vapor method, or a vacuum evaporation method may be used, but is not limited thereto. And, the above-mentioned compound may be used for forming the organic functional material layer by, for example, a vacuum deposition method, a vacuum evaporation method, or a solution coating method. In this regard, the solution coating method means spin coating, dip coating, spray printing, screen printing, spray coating, and roll coating, but is not limited thereto. Vacuum evaporation means heating and plating a material onto a substrate in a vacuum environment. In the present invention, the respective layers are preferably formed by a vacuum vapor deposition method.
The material for forming each layer according to the present invention may be used as a single layer by forming a film alone, or may be used as a single layer by forming a film after mixing with another material, or may be a laminated structure between layers formed by forming a film alone, a laminated structure between layers formed by mixing, or a laminated structure between layers formed by forming a film alone and layers formed by mixing.
It is noted that the exemplary embodiments have been disclosed herein and that, although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation. The features, characteristics and/or elements described in connection with a particular embodiment may be used alone or in combination with the features, characteristics and/or elements described in connection with other embodiments unless specified otherwise.
Examples
The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.
The known materials used in examples and comparative examples were purchased from energy saving ten thousand, inc.
Intermediate Synthesis example 1
Intermediate G-1 synthesis:
(1) Preparing a three-necked flask, adding 0.01mol of raw material A-1 and 0.015mol of raw material B-1 under an atmosphere of nitrogen, dissolving in a mixed solvent (90 ml of toluene, 45ml of ethanol), and then adding 0.03mol of Na 2 CO 3 The aqueous solution (2M) was stirred for 1 hour with nitrogen, and then 0.0001mol Pd (PPh) 3 ) 4 Reflux was performed for 15 hours, the spot plate was sampled and the reaction was complete. Naturally cooling, filtering, rotary steaming filtrate, and passing through a silica gel column to obtain an intermediate J-1, wherein the purity is 96.4%, and the yield is 83.7%. Elemental analysis structure (molecular formula C) 18 H 14 BBrClN): theoretical value C,58.36; h,3.81; b,2.92; br,21.57; cl,9.57; n,3.78; test value C,58.35; h,3.86; b,2.91; br,21.55; cl,9.56; n,3.79.ESI-MS (M/z) (m+): theoretical 369.01 and measured 369.59.
(2) Taking 0.1mol of intermediate J-1 and 0.12mol of benzene, adding 0.12mol of tertiary butyl lithium, 120ml of tertiary butyl benzene, preserving heat for 2 hours at 60 ℃, cooling to room temperature, and dropwise adding 0.12mol of BBr 3 Fully reacting for half an hour, adding water, precipitating solid, washing by n-hexane in sequence, and recrystallizing by ethanol to obtain an intermediate G-1.HPLC purity 96.3%,the yield thereof was found to be 79.7%. Elemental analysis structure (molecular formula C) 30 H 20 B 2 BrN): theoretical value C,72.64; h,4.06; b,4.36; br,16.11; n,2.82; test value C,72.65; h,4.08; b,4.35; br,16.13; n,2.81.ESI-MS (M/z) (m+): theoretical 495.10 and measured 495.39.
Intermediate Synthesis example 2
Intermediate G-8 synthesis:
(1) In a three-necked flask, under the protection of nitrogen, 0.02mol of raw material A, 0.024mol of raw material B, 0.04mol of sodium tert-butoxide and 1X 10 are added -4 mol Pd 2 (dba) 3 、1×10 -4 Heating and refluxing mol tri-tert-butyl phosphorus and 150ml toluene for 24 hours, sampling a spot plate, and completely reacting; naturally cooling, filtering, rotary steaming filtrate, and column chromatography to obtain intermediate S1, wherein the purity of HPLC is 99.1%, and the yield is 65.1%;
(2) Adding 0.01mol of raw material C, 0.012mol of tertiary butyl lithium and 150ml of tertiary butyl benzene into a three-port bottle under the protection of nitrogen, stirring and mixing, heating to 60 ℃, and stirring and reacting for 2h; then naturally cooling to room temperature, and dropwise adding 0.012mol of BBr 3 And 0.05mol of diisopropylethylamine, stirring and reacting for 1h, sampling a spot plate, and displaying that no intermediate S1 remains, wherein the reaction is complete; naturally cooling to room temperature, adding water and dichloromethane for extraction and liquid separation; taking an organic phase, adding anhydrous magnesium sulfate for dewatering, filtering, performing reduced pressure rotary evaporation (-0.09 MPa,25 ℃) on the filtrate, and passing through a neutral silica gel column to obtain a target product, wherein the HPLC purity is 99.0%, and the yield is 47.1%;
elemental analysis structure (molecular formula C) 41 H 43 BClNO): theoretical value C,80.46; h,7.08; b,1.77; cl,5.79; n,2.29; o,2.61; test value: c,80.47; h,7.06; b,1.81; cl,5.80, N,2.27; o,2.59.ESI-MS (M/z) (m+): theoretical 611.31 and measured 611.46.
Intermediate G was prepared by the synthetic method of intermediates G-1 and G-8, and the specific structures are shown in Table 1.
TABLE 1
Material synthesis example 1
Synthesis of compound BH 10:
adding 0.01mol of raw material 1-1,0.012mol of raw material 2-1 and 220ml of toluene into a three-port bottle under the protection of argon, stirring and mixing, 110ml of sodium carbonate aqueous solution, heating, refluxing and stirring for 8 hours; naturally cooling to room temperature, extracting the reaction solvent with toluene, removing the water layer, filtering, steaming the filtrate until no fraction is present, and passing through a neutral silica gel column to obtain BH10; HPLC purity 99.43%, yield 69.3%; elemental analysis structure (molecular formula C) 46 H 30 ): theoretical C,94.81; h,5.19; test value: c,94.79; h,5.16; . ESI-MS (M/z) (m+): theoretical 582.23 and measured 582.20.
Material synthesis example 2
Synthesis of compound BH 12:
compound BH12 was synthesized as in material synthesis example 1; HPLC purity 99.63%, yield 72.31%; elemental analysis structure (molecular formula C) 46 H 28 O): theoretical C,92.59; h,4.73; o,2.68; test value: c,92.58; h,4.70; o,2.66.ESI-MS (M/z) (m+): theoretical 596.21 and measured 596.22.
Material synthesis example 3
Synthesis of compound BH 13:
Compound BH13 was synthesized as in material synthesis example 1; HPLC purity 99.43%, yield 69.3%; elemental analysis structure (molecular formula C) 50 H 30 O): theoretical value C,92.85; h,4.68, O,2.47. Test value: c,92.81; h,4.66; o,2.45.ESI-MS (M/z) (m+): theoretical 646.23 and measured 646.20.
Material synthesis example 4
Synthesis of compound BH 47:
compound BH47 was synthesized as in material synthesis example 1; HPLC purity 98.93%, yield 71.23%; elemental analysis structure (molecular formula C) 32 H 20 N 2 ): theoretical value C,88.86; h,4.66; n,6.48; test value: c,88.89; h,4.68; n,6.50.ESI-MS (M/z) (m+): theoretical 432.16 and measured 432.18.
Material synthesis example 5
Synthesis of compound BH 64:
compound BH64 was synthesized according to the procedure of material synthesis example 1; HPLC purity 98.69%, yield 71.3%; elemental analysis structure (molecular formula C) 32 H 20 N 2 ): theoretical value C,88.86; h,4.66; n,6.48; test value: c,88.88; h,4.68; . ESI-MS (M/z) (m+): theoretical 432.16 and measured 432.18.
Material synthesis example 6
Synthesis of compound BH 67:
compound BH67 was synthesized as in material synthesis example 1; HPLC purity 99.22%, yield 72.6%; elemental analysis structure (molecular formula C) 46 H 30 ): theoretical C,94.81; h,5.19; test value: c,94.86; h,5.23; . ESI-MS (M/z) (m+): theoretical 582.23 and measured 582.28.
Material synthesis example 7
Synthesis of Compound DP-2:
in a 250ml three-necked flask, under the protection of nitrogen gas, 0.01mol of intermediate G-1,0.012mol of raw material C1 and 150ml of toluene were added and mixed with stirring, and then 5X 10 was added -5 molPd 2 (dba) 3 ，5×10 -5 mol P(t-Bu) 3 Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, sampling a dot plate, and displaying no bromide to remain, wherein the reaction is complete; naturally cooling to room temperature, filtering, steaming the filtrate until no fraction exists, and passing through a neutral silica gel column to obtain the target product, wherein the HPLC purity is 99.76%, and the yield is 76.1%. Elemental analysis structure (molecular formula C) 52 H 34 B 2 N 4 ): theoretical value C,84.80; h,4.65; b,2.94; n,7.61; test value C,84.84; h,4.63; b,2.93; n,7.60.HPLC-MS: the molecular weight of the material was 736.30 and found to be 736.48.
Material synthesis example 8
Synthesis of Compound DP-72:
0.01mol of intermediate G-5 and 0.012mol of raw material C5 were dissolved in 150mL (V toluene: V ethanol=5:1) mixed solution of toluene and ethanol, and 0.0002mol of Pd (PPh) was added after oxygen removal 3 ) 4 And 0.02mol Na 2 CO 3 Reacting for 24 hours at 110 ℃ in the atmosphere of nitrogen, sampling a spot plate, cooling and filtering after the raw materials are completely reacted, removing the solvent by rotary evaporation of filtrate, and passing the crude product through a silica gel column to obtain a target product; elemental analysis structure (molecular formula C) 66 H 45 B 2 N 3 ): theoretical value C,87.91; h,5.03; b,2.40; n,4.66; test value C,87.93; h,5.06; b,2.41; n,4.65.HPLC-MS: the molecular weight of the material was 901.38 and found to be 901.27.
Material synthesis example 9
Synthesis of Compound DP-76:
prepared by the method of synthesis of compound DP-2 in material synthesis example 107, except that intermediate G-6 was used instead of intermediate G-1 and starting material C6 was used instead of starting material C1; elemental analysis structure (molecular formula C) 65 H 42 B 2 N 4 ): theoretical value C,86.68; h,4.70; b,2.40; n,6.22; test value C,86.72; h,4.66; b,2.41; n,6.21.HPLC-MS: the molecular weight of the material was 900.36 and found to be 900.21.
Material synthesis example 10
Synthesis of Compound DP-77:
prepared by the method of synthesis of compound DP-72 of material synthesis example 8, except that intermediate G-6 was used in place of intermediate G-5 and starting material C7 was used in place of starting material C5; elemental analysis structure (molecular formula C) 60 H 33 B 2 N 3 O 2 ): theoretical value C,84.83; h,3.92; b,2.54; n,4.95; test value C,84.84; h,3.91; b,2.52; n,4.96.HPLC-MS: the molecular weight of the material was 849.28 and found to be 849.48.
Material synthesis example 11
Synthesis of Compound DP-97:
prepared by the method of synthesis of compound DP-2 of material synthesis example 7, except that intermediate G-6 was used in place of intermediate G-1 and starting material C9 was used in place of starting material C1; elemental analysis structure (molecular formula C) 57 H 38 B 2 N 4 ): theoretical value C,85.52; h,4.78; b,2.70; n,7.00; test value C,85.54; h,4.79; b,2.67; n,7.01.HPLC-MS: the molecular weight of the material was 800.33, and the molecular weight was 800.23.
Material synthesis example 12
Synthesis of Compound DP-120:
prepared by the method of synthesis of compound DP-2 of material synthesis example 7, except that intermediate G-7 was used in place of intermediate G-1 and starting material C10 was used in place of starting material C1; elemental analysis structure (molecular formula C) 52 H 33 B 2 N 3 ): theoretical value C,86.57; h,4.61; b,3.00; n,5.82; test value C,86.59; h,4.60; b,3.02; n,5.80.HPLC-MS: the molecular weight of the material was 721.29 and found to be 721.46.
Material synthesis example 13
Synthesis of Compound DP-139:
in a 250ml three-port bottle, adding 0.01mol of intermediate G1, 0.012mol of tertiary butyl lithium and 150ml of tertiary butyl benzene under the protection of nitrogen, stirring and mixing, heating to 60 ℃, and stirring and reacting for 2h; then naturally cooling to room temperature, dropwise adding 0.012mol of BBR3 and 0.05mol of diisopropylethylamine, stirring at room temperature for reaction for 1h, sampling a dot plate, and displaying no intermediate G-8 left, wherein the reaction is complete; adding water and dichloromethane for extraction and liquid separation; taking outAdding anhydrous magnesium sulfate into the organic phase to remove water, filtering, performing reduced pressure rotary evaporation (-0.09 MPa,25 ℃) on the filtrate, and passing through a neutral silica gel column to obtain a target product, wherein the HPLC purity is 99.1%, and the yield is 45.7%; elemental analysis structure (molecular formula C) 41 H 41 B 2 NO): theoretical C,84.12; h,7.06; b,3.69; n,2.39; o,2.73; test value: c,84.13; h,7.05; b,3.68; n,2.40; o,2.74.ESI-MS (M/z) (m+): theoretical 585.34 and measured 585.45.
Material synthesis example 14
Synthesis of Compound DP-146:
prepared by the method of synthesis of compound DP-139 of material synthesis example 13, except that intermediate G-9 was used in place of intermediate G-8. Elemental analysis structure (molecular formula C) 36 H 24 B 2 N 2 ): theoretical value C,85.42; h,4.78; b,4.27; n,5.53; test value: c,85.43; h,4.76; b,4.28; n,5.54.ESI-MS (M/z) (m+): theoretical 506.21 and measured 506.22.
Material synthesis example 15
Synthesis of Compound DP-167:
prepared by the method of synthesis of compound DP-139 of material synthesis example 13, except that intermediate G-10 was used in place of intermediate G-8.
Elemental analysis structure (molecular formula C) 44 H 28 B 2 N 2 ): theoretical value C,87.16; h,4.65; b,3.57; n,4.62; test value: c,87.17; h,4.67; b,3.55; n,4.63.ESI-MS (M/z) (m+): theoretical 606.24 and measured 606.36.
Detection method
HOMO energy level: the measurement is carried out by an IPS measurement method, and the specific measurement steps are as follows:
the vacuum evaporation equipment is utilized to control the evaporation rate to be at the pressure of 1.0E-5Pa Evaporating a sample on an ITO substrate, wherein the film thickness of the sample is 60-80nm; the HOMO energy level of the sample film was then measured using an IPS-3 measuring apparatus, measuring environment 10 -2 A vacuum atmosphere of Pa or less.
Eg energy level: a tangent line is drawn based on the ascending side of the ultraviolet spectrophotometry (UV absorption) baseline and the first absorption peak of the single film of the sample, and the value of the intersection point of the tangent line and the baseline is used for calculation.
LUMO energy level: calculated based on the difference between the HOMO and Eg energy levels.
S1, T1 energy level: based on the actual measurement of a low-temperature fluorescence spectrometer.
Work function of electrode material: the surface work function tester developed by Shanghai university was used for testing in an atmospheric environment.
Hole mobility, electron mobility: the materials were fabricated as single charge devices and measured using a single charge fitting method.
Table 2 shows that the HOMO energy levels, LUMO energy levels, singlet energy levels (S1) and triplet energy levels (T1) of the host material and the dopant material in the present invention are characterized and tested:
TABLE 2
Preparation of organic electroluminescent device
The molecular structural formula of the related material is shown as follows:
example 1
The organic electroluminescent device is prepared according to the following steps:
a) Using transparent glass as a substrate, coating ITO with the thickness of 150nm as an anode layer on the transparent glass, respectively ultrasonically cleaning the transparent glass with deionized water, acetone and ethanol for 15 minutes, and then treating the transparent glass in a plasma cleaner for 2 minutes;
b) On the washed anode layer, hole transport material HT-1 and P-type doped material P1 are respectively placed in two evaporation sources, and the vacuum degree is 1.0E -5 Controlling the evaporation rate of HT-1 to be under the pressure PaThe evaporation rate of the P-type doping material is +.>Co-steaming to form a hole injection layer with the thickness of 10nm;
c) Evaporating a hole transport layer on the hole injection layer in a vacuum evaporation mode, wherein the hole transport layer is made of HT-1 and has a thickness of 125nm;
d) Evaporating an electron blocking layer EB-1 on the hole transport layer in a vacuum evaporation mode, wherein the thickness of the electron blocking layer EB-1 is 10nm;
e) Evaporating a luminescent layer material on the electron blocking layer by vacuum evaporation, wherein a host material is BH1, a guest material is DP-2, the mass ratio is 95:5, and the thickness is 25nm;
f) Evaporating LG201 and Liq on the light-emitting layer by a vacuum evaporation mode, wherein the mass ratio of LG201 to Liq is 50:50, the thickness is 40nm, and the layer is used as an electron transport layer;
g) Evaporating LiF on the electron transport layer by vacuum evaporation, wherein the thickness of the LiF is 1nm, and the layer is an electron injection layer;
h) On the electron injection layer, mg having a film thickness of 15nm was produced by a vacuum vapor deposition apparatus: the mass ratio of Mg to Ag in the Ag electrode layer is 1:9, and the Ag electrode layer is used as the cathode layer 10. On the cathode layer 10, CPL of 70nm was vacuum deposited as a coating layer 10.
Examples 2 to 20
The procedure of example 1 was followed, except that in step e) the host material BH1 was replaced with any one of BH10, BH12, BH13, BH26, BH36, BH47, BH64, BH 67; the doping material DP-2 is replaced by any one of DP-72, DP-76, DP-77, DP-97, DP-120, DP-139, DP-146 and DP-167.
Comparative example 1
The procedure of example 1 is followed, except that in step e) the host material is replaced with RBH; the doping material was replaced with RDP and the specific device structure is shown in table 3.
TABLE 3 Table 3
The results of measuring the performance of the devices of examples 1 to 42 and comparative example 1 are shown in Table 4.
TABLE 4 Table 4
Note that: the voltage, current efficiency and color coordinates were tested using an IVL (Current-Voltage-Brightness) test system (Freund's scientific instruments, st. John) with a current density of 10mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The life test system is an EAS-62C OLED device life tester of Japanese system technical research company;LT97 refers to the time taken for the device brightness to decay to 97% of the original brightness.
As can be seen from the results of table 4, the driving voltage of the device prepared by the host material and the doping material of the present invention is significantly reduced, and the luminous efficiency and the lifetime are significantly improved. Mainly because the dinaphthyl anthracene compound is used as a main material, the dinaphthyl anthracene compound has better TTF effect, improves the utilization rate of triplet excitons, and further enhances the luminous efficiency of the device; meanwhile, the device has a faster carrier migration rate, and can effectively reduce the voltage of the device. The doped material taking boron as the core has higher Tg, and the stability of the device can be greatly improved.
Claims (10)
1. An organic electroluminescent device, which sequentially comprises a substrate, a first electrode, an organic functional material layer and a second electrode from bottom to top, wherein the organic functional material layer comprises:
a hole transport region located over the first electrode;
a light emitting layer over the hole transport region, the light emitting layer comprising a host material and a dopant material;
an electron transport region located over the light emitting layer;
and a cover layer over the second electrode;
the method is characterized in that: wherein the light-emitting layer comprises a host material represented by the following general formula (1) and a doping material represented by the general formula (2);
wherein the host material is an anthracene compound having a general formula (1),
Z、Z 1 and Z 2 Each occurrence of which is independently represented by N or C-R, which may be the same or different, R is independently represented by a hydrogen atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the doping material is selected from one of the general formula (2):
in the general formula (2), W 1 、W 2 、W 3 Each independently of the other is represented by a nitrogen atom or a boron atom, and W 1 、W 2 、W 3 Wherein only one of the two is represented by a nitrogen atom;
a. b, c, d, e are each independently represented as 0 or 1, and a+b+c+d+e is not less than 1;
X 1 、X 2 、X 3 、X 4 、X 5 independently represents a single bond, a sulfur atom, an oxygen atom,N(R 6 )、B(R 7 )、C(R 8 )(R 9 ) Or Si (R) 10 )(R 11 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 8 And R is R 9 、R 10 And R is R 11 Can be connected with each other to form a ring;
X 1 、X 2 、X 3 、X 4 、X 5 at least one of which is not represented by a single bond;
α, β, γ, η, θ are each independently represented as 1, 2 or 3;
Y 1 to Y 21 Each independently represents a carbon atom, a nitrogen atom or C-R;
r is hydrogen atom, deuterium, tritium, cyano, halogen atom, C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 6 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups;
l is independently represented by a single bond, C 6 -C 30 Arylene, substituted or unsubstituted C 3 -C 30 Is a heteroarylene group;
R 1 to R 5 Each independently represents a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, or C 1 -C 20 Alkyl, C 1 -C 20 Alkyl-substituted silyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 5 -C 30 Heteroaryl, C 6 -C 30 Aryl or C of (2) 3 -C 30 One of the heteroaryl-substituted amine groups; r is R 1 To R 5 The connection mode with the general formula (2) comprises two modes of ring combination and substitution, wherein asterisks in the general formula (2) represent connectable sites;
the R is 6 -R 11 Respectively and independently denoted as C 1 -C 20 Alkyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 3 -C 30 Is one of the heteroaryl groups of (2); r is R 6 、R 7 Can be linked to an adjacent group and form a ring structure;
the substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Substituted or unsubstituted C 3 -C 30 Heteroaryl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 6 -C 30 Heteroaryl, substituted or unsubstituted C 3 -C 30 Heteroaryl, substituted or unsubstituted C 5 -C 30 The substituents of the heteroaryl groups are optionally selected from protium, deuterium, tritium, cyano, fluorine atoms, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (2)；
The heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
2. The organic electroluminescent device according to claim 1, wherein the doping material is represented by the following general formula (3):
wherein the symbols have the same meaning as defined in claim 1.
3. The organic electroluminescent device according to claim 1, wherein the host material is represented by one of the following general formulae (4) to (6),
in the general formulae (4) to (6),
Z、Z 1 and Z 2 Each occurrence of which is independently represented by N or C-R, which may be the same or different, R is independently represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Substituted or unsubstituted C 3 -C 30 Is optionally substituted by heteroarylSelected from protium, deuterium, tritium, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
4. The organic electroluminescent device according to claim 2, wherein the host material is represented by one of the following general formulae (7) to (9),
In the general formulae (7) to (9),
R 1 ～R 14 and Ra, rb are each independently represented by a hydrogen atom, a deuterium atom, a tritium atom, a cyano group, a substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, amino, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Heteroaryl of (a);
the substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl, substituted or unsubstituted C 1 -C 20 Alkoxy, substituted or unsubstituted C 6 -C 30 Or substituted or unsubstituted C 3 -C 30 Optionally substituted by protium, deuterium, tritium, C 1 -C 20 Alkyl, C of (2) 6 -C 30 Aryl, C of (2) 3 -C 30 One or more of the heteroaryl groups of (a);
the heteroatoms in the heteroaryl group are any one or more selected from oxygen atoms, sulfur atoms, or nitrogen atoms.
5. The device according to claim 1The organic electroluminescent device is characterized in that: the X is 1 、X 2 、X 3 、X 4 、X 5 At least one of which is represented as N (R 6 )。
6. The organic electroluminescent device of claim 1, wherein: the X is 1 、X 2 、X 3 、X 4 、X 5 At least two of which are represented as N (R 6 )。
7. The organic electroluminescent device of claim 1, wherein: the host material may be selected from the following structural features:
One of them.
8. The organic electroluminescent device of claim 1, wherein: the doping material may be selected from the following structural features:
9. the organic electroluminescent device of claim 1, wherein: the HOMO energy level of the host material is between 5.8 and 6.0eV, the LUMO energy level is between 2.9 and 3.0eV, the singlet energy level is between 2.95 and 3.15eV, and the triplet energy level is between 1.65 and 1.75 eV.
10. The organic electroluminescent device of claim 1, wherein: the proportion relation between the host material and the doping material is 99:1-70:30 based on mass.
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| JP2015128115A (en) * | 2013-12-27 | 2015-07-09 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Organic electroluminescence device |
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