阅读说明：本技术 一种电子注入材料及有机发光器件 (Electron injection material and organic light-emitting device ) 是由 潘龙鑫 张正川 代好 叶添昇 汪奎 于 2020-07-31 设计创作，主要内容包括：本发明提供了一种电子注入材料,如式(I)所示；其中,所述R<Sub>1</Sub>与R<Sub>2</Sub>各自独立地为取代或未取代的烷胺基、取代或未取代的杂环基及其衍生物基团。与现有技术相比,本发明提供的金刚烷类有机碱以金刚烷胺为核心,同时连接可传输电子类型的结构作为电子注入材料,其可与电子传输材料形成氢键,实现高的电子注入能力,其而不需要考虑电离能,并且该电子注入材料合成简单,分子稳定,在保证形成氢键的同时分子也具有柔性支链,方便制成喷墨型材料,不仅可用于蒸镀直接镀膜,还可采用喷墨形式进行器件的制作,有助于降低成本。(The invention provides an electron injection material, which is shown as a formula (I); wherein, R is 1 And R 2 Each independently is a substituted or unsubstituted alkylamino group, a substituted or unsubstituted heterocyclic group, and a derivative group thereof. Compared with the prior art, the adamantane organic base provided by the invention takes amantadine as a core, is simultaneously connected with an electron-transmissible type structure to serve as an electron injection material, can form a hydrogen bond with the electron transport material, realizes high electron injection capability without considering ionization energy, is simple to synthesize, has stable molecules, ensures the formation of the hydrogen bond, has flexible branched chains on the molecules, is convenient to prepare into an ink-jet type material, and can be used for directly coating a film by evaporationAnd the device can be manufactured in an ink jet mode, so that the cost is reduced.)

1. An electron injecting material, characterized by the formula (I):

wherein, R is₁And R₂Each independently is a substituted or unsubstituted alkylamino group, a substituted or unsubstituted heterocyclic group, and a derivative group thereof.

2. The electron injection material of claim 1, wherein the substituted or unsubstituted alkylamino groups are selected from substituted or unsubstituted alkylamino groups of C1 to C20; the substituent of the substituted alkylamino is selected from one or more of halogen, cyano, alkylamino of C1-C10 and alkoxy of C1-C10.

3. The electron injection material of claim 1, wherein the substituents in the substituted heterocyclic group and the derivative group thereof are selected from one or more of halogen, alkyl group of C1 to C10, alkoxy group of C1 to C10, cyano group, and substituted and unsubstituted nitrogen-containing heterocyclic group of C2 to C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, alkyl of C1-C10, alkoxy of C1-C10 and cyano.

4. The electron injecting material according to claim 1, wherein the hetero atom in the substituted or unsubstituted heterocyclic group and the derivative thereof is one or more selected from the group consisting of Si, S, O and N, and includes at least Si or N.

5. The electron injecting material according to claim 4, wherein the number of hetero atoms N in the substituted or substituted heterocyclic group and the derivative group thereof is 1 to 3.

6. The electron injecting material according to claim 1, wherein the substituted or unsubstituted heterocyclic group and the derivative group thereof are selected from the group consisting of substituted or unsubstituted oxazole and the derivative group thereof, substituted or unsubstituted oxadiazole and the derivative group thereof, substituted or unsubstituted pyrrole and the derivative group thereof, substituted or unsubstituted imidazole and the derivative group thereof, substituted or unsubstituted pyridine and the derivative group thereof, substituted or unsubstituted pyrazine and the derivative group thereof, substituted or unsubstituted pyrimidine and the derivative group thereof, substituted or unsubstituted benzothiazole and the derivative group thereof, substituted or unsubstituted phenanthroline and the derivative group thereof, substituted or unsubstituted quinoxaline and the derivative group thereof, substituted or unsubstituted benzodithiazole and the derivative group thereof, substituted or unsubstituted benzodioxazole and the derivative group thereof, and, Substituted or unsubstituted silole and derivatives thereof.

7. The electron injection material of claim 6, wherein the substituted or unsubstituted oxazole and its derivative groups are selected from one of the following groups:

wherein m is₁And m₂Each independently is an integer of 0 to 2;

the R is₃And R₄Each independently selected from one of halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano, and substituted and unsubstituted nitrogen-containing heterocyclic groups of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted oxadiazole and its derivative groups are selected from the following groups:

the R is₅One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted pyrrole and its derivative group is selected from the following groups:

m₃is an integer of 0 to 3;

the R is₆And R₇Each independently selected from one of halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano, and substituted and unsubstituted nitrogen-containing heterocyclic groups of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted imidazole and its derivative group is selected from the following groups:

m₄is an integer of 0 to 2;

the R is₈One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted pyridine and the derivative group thereof are selected from one of the following groups:

m₅is an integer of 0 to 4;

the R is₉One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted pyrazine and derivative group thereof is selected from one of the following groups:

m₆is an integer of 0 to 3; m is₇And m₇' independently of each other, an integer of 0 to 5

The R is₁₀、R₁₁And R₁₁' are respectively and independently selected from one of halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano, substituted and unsubstituted nitrogen heterocyclic groups of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted pyrimidine and derivative groups thereof are selected from one of the following groups:

m₈is an integer of 0 to 3; m is₉、m₁₀And m₁₀' are each independently an integer of 0 to 5;

the R is₁₂～R₁₄And R₁₄' are respectively and independently selected from one of halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano, substituted and unsubstituted nitrogen heterocyclic groups of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted benzothiazole and derivative group thereof is selected from one of the following groups:

m₁₁and m₁₂Each independently is an integer of 0 to 4;

the R is₁₅And R₁₆Each independently selected from one of halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano, and substituted and unsubstituted nitrogen-containing heterocyclic groups of C2-C10; the substituent in the substituted C2-C10 nitrogen heterocyclic group is selected fromOne or more selected from halogen, alkyl of C1-C10, alkoxy of C1-C10 and cyano;

the substituted or unsubstituted phenanthroline and derivative groups thereof are selected from the following groups:

m₁₃is an integer of 0 to 7;

the R is₁₇One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted quinoxaline and derivative groups thereof are selected from the following groups:

m₁₄is an integer of 0 to 5;

the R is₁₈One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted benzo-bis-thiazole and the derivative group thereof are selected from the following groups:

m₁₅is an integer of 0 to 3;

the R is₁₉One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; among the substituted nitrogen-containing heterocyclic groups of C2 to C10The substituent of (A) is selected from one or more of halogen, alkyl of C1-C10, alkoxy of C1-C10 and cyano;

the substituted or unsubstituted benzo-bis-oxazole and its derivative groups are selected from the following groups:

m₁₆is an integer of 0 to 3;

the R is₂₀One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano;

the substituted or unsubstituted silole and derivative groups thereof are selected from the following groups:

m₁₇is an integer of 0 to 3; m is₁₈Is an integer of 0 to 4;

the R is₂₁～R₂₆One selected from halogen, alkyl of C1-C10, alkoxy of C1-C10, cyano and substituted and unsubstituted nitrogen heterocyclic group of C2-C10; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is selected from one or more of halogen, alkyl of C1-C10, alkoxy of C1-C10 and cyano.

8. The electron injection material of claim 1, wherein R is₁And R₂Also, the electron injecting material is selected from one or more of the following compounds:

9. the electron injection material of claim 1, wherein R is₁And R₂In contrast, the electron injecting material is selected from one or more of the following compounds:

10. an organic light-emitting device comprising an anode, a cathode, at least one organic compound layer between the anode and the cathode; the organic compound of the organic compound layer includes at least one of the electron injecting materials as set forth in any one of claims 1 to 7.

11. The organic light-emitting device according to claim 10, wherein the organic compound layer comprises an electron injection layer containing at least one of the electron injection materials according to any one of claims 1 to 9.

12. A display panel comprising the organic light-emitting device according to any one of claims 10 to 11.

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an electron injection material and an organic light-emitting device.

Background

In recent years, the application of various novel organic semiconductor materials and novel organic semiconductor device structures makes great progress on OLED performance and industrialization, and the organic semiconductor materials have obvious advantages compared with the traditional inorganic semiconductor materials. However, the organic semiconductor material, particularly the electron transport material, has a low carrier concentration and mobility ratio, and the mobility of electrons in the organic semiconductor material is generally lower than that of holes, as shown in fig. 1(a), so that the injection and transport of electrons in the OLED are difficult compared with those of holes, and thus the electrons and holes cannot be completely recombined in the recombination region, limiting the improvement of recombination efficiency.

Improving the injection and transmission performance of electrons in the OLED is one of the key methods for reducing the operating voltage of the organic light emitting device and improving the light emitting efficiency of the device. Electrical doping is often used to improve the injection and transport properties of organic semiconductor material carriers, reduce the operating voltage of the device, improve the efficiency of the device, and the like. The so-called electrical doping is an N-type dopant added to enhance electron injection from the cathode in a carrier emission type device, since a large injection barrier exists between the Work Function (WF) of the cathode and the Lowest Unoccupied Molecular Orbital (LUMO) of an organic compound, which is generally difficult to inject electrons from the cathode, as shown in fig. 1 (b). Electron injection of conventional N-type dopants is achieved primarily by electron transfer of the dopant to the host.

The electron injection problem of OLEDs has always been a bottleneck in device technology. The most common current practice is to use the Liq system or alkali metals, the principle of which is: li⁺Bending the energy band from the cathode to the ETL so that electrons are transferred to the ETL after injection and transfer occurs; the alkali metal releases the outer electrons directly to the ETL for transmission, as shown in fig. 1 (c).

However, the weakness of the Liq system is that its transfer efficiency is a bottleneck, resulting in inferior injection properties to alkali metals; moreover, the thermodynamic property of Liq is a great challenge on the G6 line, and long-term heating inevitably cracks Liq to affect the device lifetime. The alkali metal is too active, and although the injection property is good, the alkali metal is unstable in the atmosphere and is easy to burn to cause accidents, so that the alkali metal has great potential safety hazard when used in a factory.

Disclosure of Invention

In view of the above, the present invention provides an electron injection material and an organic optoelectronic device having high and stable electron injection efficiency.

The invention provides an electron injection material, which is shown as a formula (I):

wherein, R is₁And R₂Each independently is a substituted or unsubstituted alkylamino group, a substituted or unsubstituted heterocyclic group, and a derivative group thereof. The R1 is the same as R2, and the electron injection material is selected from one or more of the following compounds:

the R1 is different from R2, and the electron injection material is selected from one or more of the following compounds:

the present invention also provides an organic light emitting device comprising an anode, a cathode, at least one organic compound layer between the anode and the cathode; the organic compound of the organic compound layer includes at least one of the above-described electron injection materials.

Preferably, the organic compound layer includes an electron injection layer containing at least one of the above-described electron injection materials.

The invention also provides a display panel comprising the organic light-emitting device.

The invention provides an electron injection material, which is shown as a formula (I); wherein, R is₁And R₂Each independently is a substituted or unsubstituted alkylamino group, a substituted or unsubstituted heterocyclic group, and a derivative group thereof. Compared with the prior art, the adamantane organic base provided by the invention takes amantadine as a core, is simultaneously connected with an electron-transmissible type structure to serve as an electron injection material, can form a hydrogen bond with the electron transport material, realizes high electron injection capability, does not need to consider ionization energy, is simple to synthesize, has stable molecules, ensures the formation of the hydrogen bond, has flexible branched chains on the molecules, is convenient to prepare an ink-jet type material, can be used for vapor deposition direct coating, can also adopt an ink-jet form to prepare a device, and is beneficial to reducing the cost.

Drawings

FIG. 1 is a schematic diagram of electron migration of an organic semiconductor material;

fig. 2 is a schematic structural diagram of an organic light emitting device provided by the present invention;

FIG. 3 is a current density curve diagram of light emitting devices obtained in examples 1 to 4 of the device of the present invention and comparative example of the device under different voltages;

FIG. 4 is a graph showing the lifetime change of the light emitting device obtained in examples 1 to 4 of the device of the present invention and comparative example of the device.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides an electron injection material, which is shown as a formula (I):

wherein, R is₁And R₂Each independently is a substituted or unsubstituted alkylamino group, a substituted or unsubstituted heterocyclic group, and a derivative group thereof.

In the present invention, the substituted or unsubstituted alkylamino group is preferably a substituted or unsubstituted alkylamino group of C1 to C20, more preferably a substituted or unsubstituted alkylamino group of C1 to C15, still more preferably a substituted or unsubstituted alkylamino group of C1 to C10, still more preferably a substituted or unsubstituted alkylamino group of C1 to C6, and most preferably a substituted or unsubstituted alkylamino group of C2 to C6; the substituent of the substituted alkylamino is preferably one or more of halogen, cyano, alkylamino of C1-C10 and alkoxy of C1-C10, more preferably one or more of halogen, cyano, alkylamino of C1-C8 and alkoxy of C1-C8, still more preferably one or more of halogen, cyano, alkylamino of C1-C6 and alkoxy of C1-C6, and most preferably one or more of fluorine atom, cyano, alkylamino of C2-C4 and alkoxy of C2-C4; the number of the substituents of the substituted alkylamino group is preferably 1 to 4, more preferably 1 to 2.

The substituted or unsubstituted heterocyclic group and the derivative group thereof are preferably substituted or unsubstituted C2-C40 heterocyclic groups and derivative groups thereof, more preferably C2-C30 heterocyclic groups and derivative groups thereof, still more preferably C2-C25 heterocyclic groups and derivative groups thereof, still more preferably C2-C20 heterocyclic groups and derivative groups thereof, still more preferably C2-C15 heterocyclic groups and derivative groups thereof, and most preferably C2-C12 heterocyclic groups and derivative groups thereof; the hetero atom in the substituted or unsubstituted heterocyclic group and the derivative group thereof is preferably one or more of Si, S, O and N, and at least comprises Si or N; in the invention, the heteroatom is an element containing lone pair electrons, so that hydrogen bonds can be added to form the heteroatom, and the electron injection property is enhanced; the number of heteroatoms in the substituted or unsubstituted heterocyclic group and the derivative group thereof is preferably 1-5, and more preferably 2-4; the number of N atoms in the substituted or unsubstituted heterocyclic group and the derivative group thereof is preferably 1-3; the number of N is increased, the corresponding alkalinity is also enhanced, and the stronger the alkalinity is, the more favorable the hydrogen bond combination among molecules is, so that the electron injection efficiency is improved; the substituent group in the substituted heterocyclic group and the derivative group thereof is preferably one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano, substituted and unsubstituted C2-C10 nitrogen-containing heterocyclic groups, more preferably one or more of halogen, C1-C8 alkyl, C1-C8 alkoxy, cyano, substituted and unsubstituted C2-C8 nitrogen-containing heterocyclic groups, further preferably one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano, substituted and unsubstituted C2-C6 nitrogen-containing heterocyclic groups, and most preferably one or more of fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, cyano, substituted and unsubstituted C2-C5 nitrogen-containing heterocyclic groups; the substituent group in the substituted C2-C10 nitrogen-containing heterocyclic group is preferably one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano, more preferably one or more of halogen, C1-C8 alkyl, C1-C8 alkoxy and cyano, still more preferably one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy and cyano, and most preferably one or more of fluorine atom, C1-C6 alkyl, C1-C6 alkoxy and cyano; when the substituent group in the substituted heterocyclic group and the derivative group thereof is a long-chain group such as a long-chain alkyl group or a long-chain alkoxy group, the solubility of the molecule can be improved, and the solubility of the molecule containing the alkane chain is generally good, which is beneficial to the preparation of ink-jet printing ink.

In the present invention, it is more preferable that, the substituted or unsubstituted heterocyclic group and the derivative group thereof are substituted or unsubstituted oxazole and the derivative group thereof, substituted or unsubstituted oxadiazole and the derivative group thereof, substituted or unsubstituted pyrrole and the derivative group thereof, substituted or unsubstituted imidazole and the derivative group thereof, substituted or unsubstituted pyridine and the derivative group thereof, substituted or unsubstituted pyrazine and the derivative group thereof, substituted or unsubstituted pyrimidine and the derivative group thereof, substituted or unsubstituted benzothiazole and the derivative group thereof, substituted or unsubstituted phenanthroline and the derivative group thereof, substituted or unsubstituted quinoxaline and the derivative group thereof, substituted or unsubstituted benzodithiazole and the derivative group thereof, substituted or unsubstituted benzodioxazole and the derivative group thereof, and substituted or unsubstituted silole and the derivative group thereof.

According to the invention, the substituted or unsubstituted oxazole and its derivative groups are preferably one of the following groups:

wherein m is₁And m₂Each independently is preferably an integer of 0 to 2, more preferably 0 or 1;

the R is₃And R₄Each independently is preferably one of halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano and substituted and unsubstituted C2-C10 nitrogen-containing heterocyclic groups, more preferably one of halogen, C1-C8 alkyl, C1-C8 alkoxy, cyano and substituted and unsubstituted C2-C8 nitrogen-containing heterocyclic groups, still more preferably one of halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano and substituted and unsubstituted C2-C6 nitrogen-containing heterocyclic groups, and most preferably one of fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, cyano and substituted and unsubstituted C2-C5 nitrogen-containing heterocyclic groups; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted oxadiazole and its derivative groups are selected from the following groups:

the R is₅Preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of a fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted pyrrole and its derivative groups are preferably the following groups:

m₃is an integer of 0 to 3, more preferably 0, 1 or 2.

The R is₆And R₇Each independently is preferably one of halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano and substituted and unsubstituted C2-C10 nitrogen-containing heterocyclic groups, more preferably one of halogen, C1-C8 alkyl, C1-C8 alkoxy, cyano and substituted and unsubstituted C2-C8 nitrogen-containing heterocyclic groups, still more preferably one of halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano and substituted and unsubstituted C2-C6 nitrogen-containing heterocyclic groups, and most preferably one of fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, cyano and substituted and unsubstituted C2-C5 nitrogen-containing heterocyclic groups; the substituted C2-C10 nitrogen-containing heterocyclic groupThe substituent(s) in (b) is preferably one or more of halogen, alkyl group having from C1 to C10, alkoxy group having from C1 to C10 and cyano group, more preferably one or more of halogen, alkyl group having from C1 to C8, alkoxy group having from C1 to C8 and cyano group, still more preferably one or more of halogen, alkyl group having from C1 to C6, alkoxy group having from C1 to C6 and cyano group, and most preferably one or more of fluorine atom, alkyl group having from C1 to C6, alkoxy group having from C1 to C6 and cyano group.

The substituted or unsubstituted imidazoles and their derivative groups are preferably the following groups:

m₄is an integer of 0 to 2, more preferably 0 or 1.

The R is₈Preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of a fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted pyridine and its derivative group is preferably one of the following groups:

m₅is an integer of 0 to 4, more preferably an integer of 0 to 3, still more preferably 0, 1 or 2;

the R is₉Preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of a fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted pyrazine and derivative group thereof is preferably one of the following groups:

m₆preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0 or 1; m is₇And m₇' are each independently preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 3, and most preferably 0, 1 or 2.

The R is₁₀、R₁₁And R₁₁' independently of one another, the compound is preferably one of halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano and substituted and unsubstituted C2-C10 nitrogen-containing heterocyclic group, and more preferably halogen, C1-C8 alkyl, C1-C8 alkoxy, cyano, substituted and unsubstitutedOne of nitrogen-containing heterocyclic groups of C2 to C8, more preferably one of halogen, alkyl groups of C1 to C6, alkoxy groups of C1 to C6, cyano groups, and substituted and unsubstituted nitrogen-containing heterocyclic groups of C2 to C6, and most preferably one of fluorine atoms, alkyl groups of C1 to C6, alkoxy groups of C1 to C6, cyano groups, and substituted and unsubstituted nitrogen-containing heterocyclic groups of C2 to C5; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted pyrimidine and derivative groups thereof are preferably one of the following groups:

m₈preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0 or 1; m is₉、m₁₀And m₁₀' are each independently preferably an integer of 0 to 5, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 3, and most preferably 0, 1 or 2.

The R is₁₂～R₁₄And R₁₄' is independently preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent of the substituted nitrogen-containing heterocyclic group of C2-C10 is preferably halogen, alkyl of C1-C10,One or more of alkoxy of C1-C10 and cyano, more preferably one or more of halogen, alkyl of C1-C8, alkoxy of C1-C8 and cyano, still more preferably one or more of halogen, alkyl of C1-C6, alkoxy of C1-C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1-C6, alkoxy of C1-C6 and cyano.

The substituted or unsubstituted benzothiazole and derivative group thereof is preferably one of the following groups:

m₁₁and m₁₂Each independently is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and still more preferably 0, 1 or 2.

The R is₁₅And R₁₆Each independently is preferably one of halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano and substituted and unsubstituted C2-C10 nitrogen-containing heterocyclic groups, more preferably one of halogen, C1-C8 alkyl, C1-C8 alkoxy, cyano and substituted and unsubstituted C2-C8 nitrogen-containing heterocyclic groups, still more preferably one of halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano and substituted and unsubstituted C2-C6 nitrogen-containing heterocyclic groups, and most preferably one of fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, cyano and substituted and unsubstituted C2-C5 nitrogen-containing heterocyclic groups; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted phenanthroline and derivative groups thereof are preferably the following groups:

m₁₃preferably an integer of 0 to 7, more preferably an integer of 0 to 6, further preferably an integer of 0 to 5, further preferably an integer of 0 to 4, further preferably an integer of 0 to 3, and most preferably 0, 1 or 2.

The R is₁₇Preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of a fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted quinoxaline and derivative groups thereof are preferably the following groups:

m₁₄preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 3, and most preferably 0, 1 or 2.

The R is₁₈Preferably one of halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano and substituted and unsubstituted C2-C10 nitrogen-containing heterocyclic ring groups, more preferably halogen, C1-C8 alkyl, C1-C8 alkoxy, cyano and substituted and unsubstituted C2-C8 nitrogen-containing heterocyclic ring groupsAmong them, further preferably halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano, substituted and unsubstituted C2-C6 nitrogen-containing heterocyclic group, most preferably fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, cyano, substituted and unsubstituted C2-C5 nitrogen-containing heterocyclic group; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted benzodithiazole and derivative groups thereof are preferably the following groups:

m₁₅preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.

The R is₁₉Preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of a fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent in the substituted C2-C10 nitrogen-containing heterocyclic group is preferably one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy and cyano, more preferably one or more of halogen, C1-C8 alkyl, C1-C8 alkoxy and cyano, still more preferably one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy and cyano, and most preferablyPreferably one or more of fluorine atom, C1-C6 alkyl, C1-C6 alkoxy and cyano.

The substituted or unsubstituted benzobisoxazole and its derivative groups are preferably the following groups:

m₁₆preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.

The R is₂₀Preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of a fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

The substituted or unsubstituted silole and derivatives thereof are preferably the following groups:

m₁₇is an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1; m is₁₈Preferably an integer of 0 to 4, more preferably an integer of 0 to 3, further preferably an integer of 0 to 2, and most preferably 0 or 1.

The R is₂₁～R₂₆Preferably one of halogen, alkyl of C1 to C10, alkoxy of C1 to C10, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C10, more preferably one of halogen, alkyl of C1 to C8, alkoxy of C1 to C8, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C8, still more preferably one of halogen, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C6, and most preferably one of a fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6, cyano, and a nitrogen-containing heterocyclic group of substituted and unsubstituted C2 to C5; the substituent group in the substituted nitrogen-containing heterocyclic group of C2 to C10 is preferably one or more of halogen, alkyl of C1 to C10, alkoxy of C1 to C10 and cyano, more preferably one or more of halogen, alkyl of C1 to C8, alkoxy of C1 to C8 and cyano, still more preferably one or more of halogen, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano, and most preferably one or more of fluorine atom, alkyl of C1 to C6, alkoxy of C1 to C6 and cyano.

According to the invention, said R₁And R₂May be the same or different; when the first asymmetry of the functional groups can effectively enhance the solubility of the material, if the related ink can be researched according to the characteristics in the following realization of ink-jet printing, the second asymmetry structure can reduce the solubility of the electron injection material, and the cleaning efficiency and the cleaning quality can be improved in the Mask cleaning process.

Most preferably, when said R is₁And R₂Meanwhile, the electron injection material is selected from one or more of the following compounds:

when R is₁And R₂In contrast, the electron injecting material is selected from one or more of the following compounds:

the adamantane organic base provided by the invention takes amantadine as a core, is simultaneously connected with an electron-transmissible type structure to serve as an electron injection material, can form a hydrogen bond with the electron transmission material, realizes high electron injection capability, does not need to consider ionization energy, is simple to synthesize, has stable molecules, ensures the formation of the hydrogen bond, has flexible branched chains on the molecules, is convenient to prepare into an ink-jet type material, can be used for vapor deposition direct coating, can also adopt an ink-jet form to prepare a device, and is beneficial to reducing the cost.

The invention also provides a preparation method of the electron injection material, which comprises the following steps: reacting the compound shown in the formula (II) with the compound shown in the formula (III) to obtain R₁And R₂A compound represented by the formula (I) wherein the substituents are the same;

or, the compound shown in the formula (II) is firstly reacted with the compound shown in the formula (III) and then reacted with the compound shown in the formula (IV) to obtain R₁And R₂A compound represented by the formula (I) wherein the substituents are different;

or, the compound shown in the formula (II) is firstly reacted with the compound shown in the formula (IV) and then reacted with the compound shown in the formula (III) to obtain R₁And R₂A compound represented by the formula (I) wherein the substituents are different.

Wherein, X is halogen, preferably Br; the R is₁And R₂Are all the sameAs mentioned above, no further description is provided herein.

The present invention also provides an organic light emitting device comprising an anode, a cathode, at least one organic compound layer between the anode and the cathode; the organic compound of the organic compound layer includes at least one of the electron injecting materials represented by the above formula (I); the organic compound layer preferably further includes an electron transport type organic material capable of forming an intermolecular hydrogen bond with the electron injecting material represented by formula (I); it is preferably co-doped with the electron injecting material represented by formula (I) while plating to form an organic compound layer.

Referring to fig. 2, fig. 2 is a schematic structural diagram of an organic light emitting device provided in the present invention, wherein 1 is a substrate made of glass or other suitable materials (e.g., plastic); 2 is a transparent anode such as ITO or IGZO; 3 is an organic compound layer; and 4 is a metal cathode.

Preferably, the organic compound layer further includes an electron injection layer containing at least one of the electron injection materials represented by the above formula (I).

Preferably, the organic compound layer preferably includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are sequentially provided; the electron injection layer preferably comprises an interlayer and a metal oxide; the interlayer includes at least one of the electron injecting materials represented by the above formula (I), and preferably further includes an electron transporting organic material such as OXD-7 which can form an intermolecular hydrogen bond with the electron injecting material represented by the formula (I).

The invention also provides a display panel, which comprises the organic light-emitting device; the organic light-emitting device comprises an anode, a cathode and a light-emitting layer positioned between the anode and the cathode, wherein the host material or the guest material of the light-emitting layer is one or more of the compounds disclosed by the invention.

According to one embodiment of the display panel of the present invention, the organic light emitting device further includes one or more layers of a hole injection layer, a hole transport layer, a light emitting layer, and a hole blocking layer.

In one embodiment of the display panel according to the present invention, the structure of an Organic Light Emitting Device (OLED) is schematically illustrated as fig. 2. Wherein 1 is a substrate (substrate) made of glass or other suitable materials (such as plastics); 2 is a transparent anode such as ITO or IGZO; 3 is an organic film layer (including a luminescent layer); and 4, metal cathodes which jointly form a complete OLED device. The two electrodes 2 and 4 may be interchanged.

In the display panel provided by the present invention, the anode material of the organic light emitting device may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, and the like, and alloys thereof. The anode material may also be selected from metal oxides such as indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; the anode material may also be selected from conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), and the like. In addition, the anode material may be selected from materials that facilitate hole injection in addition to the listed anode materials and combinations thereof, including known materials suitable for use as anodes.

In the display panel provided by the present invention, the cathode material of the organic light emitting device may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof. The cathode material may also be selected from multi-layered metallic materials such as LiF/Al, LiO₂/Al、BaF₂Al, etc. In addition to the cathode materials listed above, the cathode materials can also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as cathodes.

The organic light emitting device may be fabricated according to a method well known in the art and will not be described in detail herein. In the present invention, the organic light emitting device can be fabricated by: an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer. The organic thin layer can be formed by a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or the like.

In the present invention, # denotes the position of the connecting bond unless otherwise specified.

In order to further illustrate the present invention, the following describes an electron injection material and an organic light emitting device in detail with reference to the following examples.

The reagents used in the following examples are all commercially available.