阅读说明：本技术 一种有机化合物及包含该化合物的有机电致发光器件 (Organic compound and organic electroluminescent device containing same ) 是由 段炼 张东东 刘子扬 李骁 于 2021-08-18 设计创作，主要内容包括：本发明涉及一种有机有机化合物,同时涉及采用这类化合物的有机电致发光器件。本发明化合物具有下式所述的结构,R-(1)和R-(2)分别独立地选自C1-C30脂肪链烃氧基、C2-C30脂肪链烃氨基、C3-C20环状脂肪链烃氨基、取代或未取代的C6～C30芳基氨基、取代或未取代的C3～C30杂芳基氨基、取代或未取代的C6-C60的芳基、取代或未取代的C3-C60的杂芳基中的一种,Q代表桥联基团。采用本发明化合物作为电子注入层材料的有机电致发光器件,表现出优异的稳定性和较高的效率。(The present invention relates to an organic compound and also to an organic electroluminescent device using the compound. The compounds of the invention have the structure as described in the formula R 1 And R 2 Each independently selected from one of C1-C30 aliphatic chain alkoxy, C2-C30 aliphatic chain hydrocarbon amino, C3-C20 cyclic aliphatic chain hydrocarbon amino, substituted or unsubstituted C6-C30 aryl amino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, and Q represents a bridging group. The organic electroluminescent device adopting the compound of the invention as an electron injection layer material shows excellent stability and higher efficiency.)

1. An organic compound having a structure represented by the following formula (1):

in the formula (1), R₁And R₂Each independently selected from one of C1-C30 aliphatic chain alkoxy, C2-C30 aliphatic chain hydrocarbon amino, C3-C20 cyclic aliphatic chain hydrocarbon amino, substituted or unsubstituted C6-C30 aryl amino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;

n is an integer of 2 to 6; q is selected from one of substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;

when the above R is₁And R₂When the substituent exists, the substituent group is one or the combination of two of deuterium, halogen, chain alkyl of C1-C30, cycloalkyl of C3-C30, cyano, nitro, alkoxy of C1-C6, thioalkoxy of C1-C6, aryl of C6-C30 and heteroaryl of C3-C60.

2. The organic compound according to claim 1, wherein when n is 2, Q is selected from one of the following substituted or unsubstituted groups: phenylene, naphthylene, anthracenylene, methyleneoxyphenyl, benzanthracene, phenanthrenylene, benzophenanthrenylene, pyrenylene, peryleneene, fluoranthenylene, naphthacene, pentacenylene, benzopyrenylene, biphenylene, benzilidene, terphenylene, quaterphenylene, fluorenylene, spirobifluorenylene, pyridylene, methyleneoxypyridinylene, pyrimidinylene, pyrazinylene, quinolylene, benzopyrazinylene, methyleneoxybenzopyrazinylene, benzopyrimidinylene, methyleneoxybenzopyrimidinylene, isoquinolinylene, methyleneoxyisoquinolinyl, bipyridinylene, terpyridyl, tetrapyridinylene, 1, 5-naphthyridinylene, furylene, thienylene, dibenzofuranylene, dibenzothiophenylene or 9-phenylcarbazolyl;

when n is an integer of 3 to 6, Q is selected from one of the following substituted or unsubstituted groups:

3. the organic compound according to claim 1, wherein when n is 2,3 or 4, Q is selected from one of the following substituted or unsubstituted groups:

4. the method of claim 1An organic compound, said R₁、R₂Each independently selected from the following substituents:

methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, dimethylamino, tetrahydropyrrole, piperidinyl, cyclohexylimino, cycloheptimino, cyclooctimino, methoxy, ethoxy, propoxy, butoxy, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, gronyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, tetrahydropyrenyl, Cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, tert-butylcarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, phenylmercapto, phenylsulfonyl, phenolyl, diphenylphosphinoxy, naphthylmercapto, naphthylsulfonyl, naphthylphenoxy, dinaphthylphosphoxy, anthracenylmercapto, anthracenylsulfonyl, anthracenyloxy, dianthranylphosphoryloxy, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, and phenanthroimidazolyl, Pyridoimidazolyl, pyrazinoyl, quinoxalimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrenyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazoanthryl, 2, 7-diazepanyl, 2, 3-diazepanyl, 1, 6-diazepanyl, 1, 8-diazepanyl, 4,5,9, 10-tetraazapiperazinyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 1,5, 7-triazabicyclo [4.4.0] dec-5-enyl, 4-methoxyphenyl, or a combination of two kinds selected from the above groups.

5. The organic compound according to claim 1, selected from the following compounds of specific structure:

6. use of a compound as claimed in any one of claims 1 to 5 as an electron injecting material in an organic electroluminescent device.

7. An organic electroluminescent device comprising a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer formed on the substrate in this order, wherein the light-emitting functional layers comprise at least one compound according to any one of claims 1 to 5;

preferably, the light emitting function layer includes a light emitting layer and an electron injecting layer, and further includes one or more of a hole injecting layer, a hole transporting layer and an electron transporting layer, the hole injecting layer is formed on the anode layer, the hole transporting layer is formed on the hole injecting layer, the light emitting layer is formed on the hole transporting layer, the electron transporting layer is formed on the light emitting layer, the electron injecting layer is formed on the electron transporting layer, and the cathode layer is formed on the electron injecting layer, wherein the electron injecting layer includes at least one compound according to any one of claims 1 to 5.

8. The organic electroluminescent device of claim 7, wherein the electron injection layer further comprises a transition metal of Ag, Au or Cu;

preferably, the electron injection layer further includes Ag.

9. The organic electroluminescent device according to claim 8, wherein the transition metal included in the electron injection layer is doped with the compound according to any one of claims 1 to 5 in a proportion of 5 wt% to 50 wt%, and the corresponding doping proportion is 0.5 vol% to 5 vol%;

preferably, the doping ratio of the transition metal to the compound of any one of claims 1 to 5 is 10 wt% to 20 wt%, and the corresponding doping ratio is 1 vol% to 2 vol%.

10. The organic electroluminescent device as claimed in any one of claims 7 to 9, wherein the electron injection layer has a total thickness of 1nm to 10 nm;

preferably, the electron injection layer has a total thickness of 3nm to 5 nm.

Technical Field

The present invention relates to an organic compound and also to an organic electroluminescent device using the compound.

Background

Organic Light Emitting Diodes (OLEDs) are a type of injection type electroluminescent device, which mainly includes electrode films and Organic functional layers sandwiched between the electrode films. And applying voltage to an electrode of the OLED device, injecting holes and electrons into the organic functional layer from the anode and the cathode respectively, transmitting the holes and the electrons to the light-emitting layer under the action of an electric field, and finally recombining in the light-emitting layer to realize light emission. Since the OLED device has many advantages of high brightness, fast response, wide viewing angle, low energy consumption, flexibility, etc., it has attracted extensive attention in the field of solid-state display and lighting technology, and is considered to be one of the most promising display technologies in the 21 st century. At present, the technology is widely applied to display panels of products such as novel lighting lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology which is fast in development, high in technical requirement and wide in application prospect.

The collocation and study of organic functional layers in OLED devices have a crucial impact on the performance of the devices. Through development and research for many years, the common functionalized organic materials at present mainly comprise: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like. Currently, the LUMO level of an electron transport material generally used in an OLED is mostly between-2.7 eV and-3.4 eV, and the work function of metal cathodes such as Al and Ag is greater than 4.0eV, so that a large injection barrier needs to be overcome when electrons are injected from the metal cathode to the LUMO level of the electron transport layer, which results in a higher driving voltage of the device, and electrons are minority carriers and holes are majority carriers in the device, and carrier imbalance can significantly reduce the efficiency and lifetime of the device. In order to reduce the electron injection barrier of the OLED device and improve the efficiency and the service life of the device, the prior OLED device widely adopts alkali metal compounds such as Liq and the like as n-type dopants, and matches nitrogen heteroaromatic ring electron transport materials and Al electrodes to improve the efficiency and the service life of the device. According to the literature disclosed so far, the mechanism of lowering the electron injection barrier potential by the alkali metal compound type n-type dopant such as LiF, Liq, etc. is mainly that, when an Al electrode is deposited, Liq reacts with Al and nitrogen heteroaromatic ring type Electron Transport Material (ETM) to generate Li due to the presence of Al and ETM⁺ETM^-Due to Li⁺ETM^-Is present on the cathode sideThe work function is greatly reduced, and the electron injection performance of the OLED device is improved. Therefore, the OLED device using an alkali metal compound such as LiF, Liq, etc. as an n-type dopant has a low operating voltage and high luminous efficiency. However, the alkali metal compound electron injection materials such as LiF and Liq often need to be matched with Al electrodes and nitrogen heteroaromatic ring electron transport materials to realize better electron injection performance, so that the application of the materials in top light emitting devices and inversion devices is greatly limited, and the service life of the devices still needs to be improved, so that the application of the materials in industrial production is limited. In order to further promote and expand the application of OLED devices, the development of new high-performance electron injection materials is of great significance.

In recent years, an n-type doping strategy based on transition metal coordination provides a new solution for developing efficient and stable electron injection materials. The n-type doping strategy based on transition metal coordination can be used for constructing an electron injection layer of an OLED device, the OLED device with high efficiency and long service life is prepared, and the method has wide development prospect. Transition metals (Ag, Cu and the like) are doped in an o-phenanthroline organic material (represented by B-Phen) with coordination capacity, and the process that the metal loses electrons is promoted through the coordination reaction between the o-phenanthroline material and the transition metals, so that the o-phenanthroline organic material can be matched with the transition metals (Ag, Cu and the like) to serve as an electron injection layer of an OLED device, the work function and the electron injection barrier of a cathode are remarkably reduced, the efficiency and the service life of the device are remarkably improved, and the driving voltage of the device is reduced.

Disclosure of Invention

Researches find that the structure and coordination property of the phenanthroline electron injection material have important influence on the performance and application of an OLED device. The invention aims to provide an organic compound which is used as an organic functional material applied to an organic electroluminescent device and can effectively reduce the driving voltage and improve the luminous efficiency of the device.

Specifically, the present invention provides an organic compound having a structure represented by the following formula (1):

in the formula (1), R₁And R₂Each independently selected from one of C1-C30 aliphatic chain alkoxy, C2-C30 aliphatic chain hydrocarbon amino, C3-C20 cyclic aliphatic chain hydrocarbon amino, substituted or unsubstituted C6-C30 aryl amino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;

in the formula (1), Q represents a bridging group for connecting n structural units with phenanthroline skeletons in the formula (1), and is selected from one of substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted C3-C30 heteroarylene;

in the formula (1), n is an integer of 2 to 6, and it should be noted that, in the n structural units having a phenanthroline skeleton, each different R is₁Each different R₂Are all independently, i.e. each R₁Which may be the same or different, each R₂May be the same or different, respectively;

when the substituent exists in the groups, the substituent is one or two of deuterium, halogen, C1-C30 chain alkyl, C3-C30 cycloalkyl, cyano, nitro, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 aryl and C3-C60 heteroaryl.

In the general formula of formula (1), in the structural unit of the same phenanthroline skeleton, R is₁And R₂There is a certain synergy between the substituents at the positions, which may be present simultaneously with different groups, i.e. R₁、R₂The same or different groups may be used independently of each other.

Specifically, in the present invention, in which n structural units having a phenanthroline skeleton are used, when R is₁、R₂When the phenanthroline structural molecules are designed into electron-donating groups, the electron cloud density and the electrostatic potential of the phenanthroline aromatic ring parent nucleus system compound molecules are increased, so that the phenanthroline structural molecules have more excellent electron injection performance, and the preparation of the phenanthroline structural molecules serving as electron injection materials can be obviously improvedThe stability of the compound molecule can be effectively improved. Therefore, the organic electroluminescent device adopting the compound of the invention can show higher device efficiency and service life.

In the present specification, the "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from the group.

In the present specification, the expression of Ca to Cb means that the group has carbon atoms of a to b, and the carbon atoms do not generally include the carbon atoms of the substituents unless otherwise specified.

In the present specification, "independently" means that the subject may be the same or different when a plurality of subjects are provided.

The hetero atom in the present invention generally refers to an atom or group of atoms selected from N, O, S, P, Si and Se, preferably N, O, S.

In the present specification, unless otherwise specified, the expression of chemical elements generally includes the concept of chemically identical isotopes, for example, carbon (C) includes¹²C、¹³C, etc., will not be described in detail.

In the present specification, unless otherwise specified, both aryl and heteroaryl groups include monocyclic and fused rings.

The monocyclic aryl group mentioned above means that the molecule contains one or at least two phenyl groups, and when the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and are linked by a single bond, such as phenyl, biphenylyl, terphenylyl, etc., for example; the fused ring aryl group means that at least two benzene rings are contained in the molecule, but the benzene rings are not independent of each other, but common ring sides are fused with each other, and exemplified by naphthyl, anthryl and the like; monocyclic heteroaryl means that the molecule contains at least one heteroaryl group, and when the molecule contains one heteroaryl group and other groups (e.g., aryl, heteroaryl, alkyl, etc.), the heteroaryl and other groups are independent of each other and are linked by a single bond, illustratively pyridine, furan, thiophene, etc.; fused ring heteroaryl refers to a fused ring of at least one phenyl group and at least one heteroaryl group, or, fused ring of at least two heteroaryl rings, illustratively quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, and the like.

In the specification, the substituted or unsubstituted C6-C60 aryl group, preferably C6-C30 aryl group, preferably the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and derivatives thereof, fluoranthryl, triphenylene, pyrenyl, perylenyl, perylene, and the like,A group of the group consisting of a phenyl group and a tetracenyl group. The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes a 1-naphthyl group or a 2-naphthyl group; the anthracene group is selected from the group consisting of 1-anthracene group, 2-anthracene group, and 9-anthracene group; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9 '-dimethylfluorene, 9' -spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracene group is selected from the group consisting of 1-tetracene, 2-tetracene, and 9-tetracene.

In the present specification, the substituted or unsubstituted C3-C60 heteroaryl group is preferably a C4-C30 heteroaryl group, preferably the heteroaryl group is a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group, a carbazolyl group and derivatives thereof, wherein the carbazolyl derivative is preferably a 9-phenylcarbazole, a 9-naphthylcarbazole benzocarbazole, a dibenzocarbazole, or an indolocarbazole.

Examples of the arylamino group having C6 to C30 mentioned in the present specification include: phenylamino, methylphenylamino, naphthylamino, anthrylamino, phenanthrylamino, biphenylamino and the like.

Examples of the heteroarylamino group having C6 to C30 mentioned in the present specification include: pyridylamino, pyrimidylamino, dibenzofuranylamino and the like.

Further, in the formula (1), when n is 2, Q is selected from one of the following substituted or unsubstituted groups: phenylene, naphthylene, anthracenylene, methyleneoxyphenyl, benzanthracene, phenanthrenylene, benzophenanthrenylene, pyrenylene, peryleneene, fluoranthenylene, naphthacene, pentacenylene, benzopyrenylene, biphenylene, benzilidene, terphenylene, quaterphenylene, fluorenylene, spirobifluorenylene, pyridylene, methyleneoxypyridinylene, pyrimidinylene, pyrazinylene, quinolylene, benzopyrazinylene, methyleneoxybenzopyrazinylene, benzopyrimidinylene, methyleneoxybenzopyrimidinylene, isoquinolinylene, methyleneoxyisoquinolinyl, bipyridinylene, terpyridyl, tetrapyridinylene, 1, 5-naphthyridinylene, furylene, thienylene, dibenzofuranylene, dibenzothiophenylene or 9-phenylcarbazolyl;

further, in the formula (1), when n is an integer of 3 to 6, Q is selected from one of the following substituted or unsubstituted groups:

further preferably, when n is 2,3 or 4, Q is selected from one of the following substituted or unsubstituted groups:

further, in the formula (1) of the present inventionR is as described₁、R₂Each independently selected from the following substituents:

methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, dimethylamino, tetrahydropyrrole, piperidinyl, cyclohexylimino, cycloheptimino, cyclooctimino, methoxy, ethoxy, propoxy, butoxy, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, gronyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, tetrahydropyrenyl, Cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, tert-butylcarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, phenylmercapto, phenylsulfonyl, phenolyl, diphenylphosphinoxy, naphthylmercapto, naphthylsulfonyl, naphthylphenoxy, dinaphthylphosphoxy, anthracenylmercapto, anthracenylsulfonyl, anthracenyloxy, dianthranylphosphoryloxy, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, and phenanthroimidazolyl, Pyridoimidazolyl, pyrazinoyl, quinoxalimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrenyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazoanthryl, 2, 7-diazepanyl, 2, 3-diazepanyl, 1, 6-diazepanyl, 1, 8-diazepanyl, 4,5,9, 10-tetraazapiperazinyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 1,5, 7-triazabicyclo [4.4.0] dec-5-enyl, 4-methoxyphenyl, or a combination of two kinds selected from the above groups.

Further, among the compounds of the general formula of the present invention, the following compounds E-1 to E-392 of specific structures can be preferably selected, and these compounds are merely representative:

another object of the present invention is to protect the use of the compounds of formula (1) above as functional materials in organic electroluminescent devices. Specifically, the compound of formula (1) of the present invention is suitable for use as an electron injection layer material in an organic electroluminescent device, and further, the compound of the present invention may form an electron injection layer of a device together with a transition metal of Ag, Au or Cu.

In the general formula of the compound of the invention, R₁And R₂Compared with the prior art compound which adopts a phenanthroline skeleton structure and does not adopt a substituent group, the compound has higher surface electrostatic potential, so that when the compound is used as an electron injection layer material in an organic electroluminescent device, the compound can be subjected to in-situ reaction with Ag, Au or Cu more efficiently in a vacuum evaporation process to generate a complex with low ionization energy. Due to R₁And R₂The organic electroluminescent device is designed to be an electron-donating group, so that the compound has stronger coordination performance, and when the compound is matched with Ag, Au or Cu and used as an electron injection material, the work function and the electron injection barrier of the cathode of the OLED device can be obviously reduced under lower doping concentration, so that the carrier injection performance can be effectively improved, and the organic electroluminescent device can obtain higher device efficiency and longer service life.

In addition, the application field of the compound of the invention is not limited to organic electroluminescent materials, and can be further expanded to the technical fields of perovskite and quantum dot light-emitting diodes, optical sensors, solar cells, organic thin film transistors and the like.

The present invention also provides an organic electroluminescent device comprising a substrate comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layers comprise the compound represented in the above general formula (1).

Specifically, one embodiment of the present invention provides an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a light-emitting layer and an electron injection layer, and further comprises one or more of a hole injection layer, a hole transport layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the light-emitting layer is formed on the hole transport layer, the electron transport layer is formed on the light-emitting layer, the electron injection layer is formed on the electron transport layer, and the cathode layer is formed on the electron injection layer, wherein the electron injection layer contains the compound shown in the general formula and the preferable specific compound.

Further preferably, in the organic electroluminescent device of the present invention, the compound of the present invention is used to form the electron injection layer together with a transition metal of Ag, Au or Cu. Further, the transition metal is preferably Ag.

In the organic electroluminescent device of the present invention, the doping ratio (mass percentage) of the transition metal to the o-phenanthroline-based organic material (ETM) of the general formula (1) of Ag to ETM is 5 wt% to 50 wt%, preferably 10 wt% to 20 wt%, and the corresponding doping ratio (volume fraction) is 0.5 vol% to 5 vol%, preferably 1 vol% to 2 vol%, that is, the organic electroluminescent device of the present invention is obtainedThe phenanthroline material is doped withThe transition metal of Ag, Au or Cu.

In the organic electroluminescent device of the present invention, the total thickness of the electron injection layer is 1nm to 10nm, more preferably 3nm to 5 nm.

The inventors have found that when the above-mentioned compound of the present invention is applied to an electron injection layer of an organic electroluminescent device, the device can obtain a high luminous efficiency, and the following is the inventors' conjecture, but the conjecture does not limit the scope of the present invention.

As shown in the following general formula (1'), the design and control of the bonding mode of the position 2 and the position 9 of the o-phenanthroline skeleton of the compound of the present invention is one of the core innovation points of the present invention. On the one hand, the phenanthroline skeleton is connected with the bridging group Q through the position 2, at the moment, a nitrogen atom at the position 1 of the phenanthroline skeleton can form an intramolecular hydrogen bond with an adjacent hydrogen atom on the bridging group, so that the sublimation property of the material is improved, and the stability of the material and the stability of devices in the evaporation process are improved. On the other hand, the position 9 on the phenanthroline skeleton is a hydrogen atom, which is beneficial to reducing the steric hindrance when the phenanthroline skeleton is coordinated with the transition metal, so that the phenanthroline skeleton has more excellent coordination performance.

The second special innovation of the compound of the present invention is that R is₁And R₂The phenanthroline ligand is designed as an electron-donating substituent, so that the electron cloud density and the electrostatic potential near a nitrogen atom in a phenanthroline skeleton can be remarkably improved, and the coordination ability of the phenanthroline skeleton and the nitrogen atom can be improved, so that the more excellent electron injection performance can be realized. Therefore, the compound with the structure of the general formula (1') has excellent coordination performance and stability, and can be applied to preparation of high-performance electron injection materials and OLED devices.

The OLED device prepared by the compound has the advantages of low driving voltage, high device efficiency, long service life and the like, and can meet the requirements of current OLED panel manufacturing enterprises on high-performance electron injection layer materials. In addition, raw materials required by the preparation of the compound are easy to obtain, and the synthesis process, the post-treatment and the purification process are simple and reliable, so that the compound is suitable for scientific research and industrial production.

Detailed Description

The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples.

Various chemicals used in the present invention, such as petroleum ether, methylene chloride, ethyl acetate, ethanol, toluene, sodium carbonate, and other basic chemical raw materials, were purchased from Shanghai Tantake Technology, Inc. The mass spectrometer used for determining the following compounds was a ZAB-HS type mass spectrometer measurement (manufactured by Micromass, UK).

The synthesis of the compounds of the present invention will be briefly described below. Firstly, commercially available 4, 7-dichloro-phenanthroline is used as a raw material, and substitution and modification are carried out on the 4,7 position of phenanthroline through suzuki coupling. And then performing multi-step conversion to perform chlorination on the position 2 of the phenanthroline skeleton, and finally connecting a plurality of phenanthroline skeletons with a bridging group through suzuki coupling to obtain a target product. For a target product in which the 4,7 position of phenanthroline is directly bonded to a heteroatom (O, N, S, etc.), 4,7 dichloro phenanthroline may be modified by base-catalyzed nucleophilic substitution (as shown in a representative synthetic pathway 2), and a corresponding target product is obtained by a similar process.

Synthetic examples

Representative synthetic route 1:

representative synthetic route 2:

more specifically, the following gives synthetic methods of representative compounds of the present invention.

Synthetic examples

Synthesis example 1:

synthesis of Compound E-1

In example 1, E1-1(2.80g, 8.48mmol), E1-2(4.65g, 19.17mmol) were placed in a 500mL round bottom flask, a mixture of toluene (150mL), ethanol (50mL) and deionized water (100mL) was used as a solvent, and Na was added₂CO₃(6.12g, 57.78mmol) and Pd (PPh)₃)₄(1.08g, 0.933mmol) was used as a catalyst, heated under reflux for 36 hours under nitrogen protection, filtered after the reaction system was cooled, and the filter cake was washed with saturated brine and ethanol in this order and further treated by a conventional method to obtain the final product E1(2.83g, 68% yield). Theoretical value of mass spectrum [ E-1+ H]: 491.22, respectively; MALDI-TOF-MS results: m/z: 491.31[ E-1+ H]. Elemental analysis results: theoretical value: c83.24%, H5.34%, N11.42%. Experimental values: 83.06% of C, 5.02% of H and 11.92% of N.

Synthesis example 2:

synthesis of Compound E-2

Firstly, the product E2-2 is obtained from E2-1 through Suzuki cross linking reaction according to the route, and then the product E2-2 is sequentially processed according to the reaction flow to obtain the product E2-4. A500 mL round bottom flask was charged with E2-4(6.46g, 17.60mmol), E1-1(2.64g, 8.00mmol), a mixture of toluene (150mL), ethanol (50mL) and deionized water (100mL) as solvent, and Na was added₂CO₃(6.12g, 57.78mmol) and Pd (PPh)₃)₄(1.08g, 0.933mmol) as catalyst, heating and refluxing for 36 hours, cooling and filtering, washing the filter cake with ethanol, dichloromethane/methanol mixed solution for several times, and further processing by conventional method to obtain final product E-2(3.22g, 54% yield). Theoretical value of mass spectrum [ E-2+ H]: 739.29, respectively; MALDI-TOF-MS results: m/z: 739.43[ E-2+ H]. Elemental analysis results: theoretical value: c87.78%, H4.64%, N7.58%. Experimental values: c87.67%, H4.68%, N7.65%.

Synthetic example 3:

synthesis of Compound E-3

This example is substantially the same as synthetic example 1 except that: in this example, E1-2 was changed to E3-1 in equal amount (mol). The target compound E-3(5.02g, 63% yield). Mass Spectrometry theoretical value [ E-3+ H ]: 939.35, respectively; MALDI-TOF-MS results: m/z: 939.43[ E-3+ H ]. Elemental analysis results: theoretical value: c89.53%, H4.50%, N5.97%. Experimental values: 89.43% of C, 4.55% of H and 6.02% of N.

Synthetic example 4:

synthesis of Compound E-4

This example is substantially the same as synthetic example 1 except that: in this example, E1-2 was changed to E4-1 in equal amount (mol). Target compound E-4(4.14g, 52% yield). Mass Spectrometry theoretical value [ E-4+ H ]: 939.35, respectively; MALDI-TOF-MS results: m/z: 939.56[ E-4+ H ]. Elemental analysis results: theoretical value: c89.53%, H4.50%, N5.97%. Experimental values: 89.51% of C, 4.54% of H and 5.95% of N.

Synthesis example 5:

synthesis of Compound E-5

This example is substantially the same as synthetic example 1 except that: in this example, E1-2 was changed to E5-1 in equal amount (mol). Target compound E-5(2.26g, 48% yield). Mass Spectrometry theoretical value [ E-5+ H ]: 555.21, respectively; MALDI-TOF-MS results: m/z: 555.33[ E-5+ H ]. Elemental analysis results: theoretical value: c73.63%, H4.73%, N10.10%, O11.54%. Experimental values: c73.67%, H4.72%, N10.13%, O11.48%.

Synthetic example 6:

synthesis of Compound E-7

This example is substantially the same as synthetic example 1 except that: in this example, E1-2 was changed to E7-1 in equal amount (mol). The target compound E-7(3.32g, 55% yield). Mass Spectrometry theoretical value [ E-7+ H ]: 711.39, respectively; MALDI-TOF-MS results: m/z: 711.49[ E-7+ H ]. Elemental analysis results: theoretical value: c77.72%, H6.52%, N15.76%. Experimental values: c77.79%, H6.48%, N15.73%.

Synthetic example 7:

synthesis of Compound E-13

This example is substantially the same as synthetic example 1 except that: in this example, E1-1 was changed to E13-2 in equal amount (mol). The target compound E-13(1.75g, 42% yield). Mass spectrum theoretical value [ E-13+ H ]: 491.22, respectively; MALDI-TOF-MS results: m/z: 491.25[ E-13+ H ]. Elemental analysis results: theoretical value: c83.24%, H5.34%, N11.42%. Experimental values: c82.95%, H5.21%, N11.84%.

Synthesis example 8:

synthesis of Compound E-14

This example is substantially the same as synthetic example 7, except that: in this example, E1-2 was changed to E2-4 in equal amount (mol). Target compound E-14(2.94g, 47% yield). Mass spectrum theoretical value [ E-14+ H ]: 739.29, respectively; MALDI-TOF-MS results: m/z: 739.36[ E-14+ H ]. Elemental analysis results: theoretical value: c87.78%, H4.64%, N7.58%. Experimental values: c87.77%, H4.62%, N7.61%.

Synthetic example 9:

synthesis of Compound E-15

This example is substantially the same as synthetic example 7, except that: in this example, E1-2 was changed to E3-1 in equal amount (mol). Target compound E-15(3.50g, 44% yield). Mass Spectrometry theoretical value [ E-15+ H ]: 939.35, respectively; MALDI-TOF-MS results: m/z: 939.48[ E-15+ H ]. Elemental analysis results: theoretical value: c89.53%, H4.50%, N5.97%. Experimental values: 89.55% of C, 4.45% of H and 5.94% of N.

Synthetic example 10:

synthesis of Compound E-16

This example is substantially the same as synthetic example 7, except that: in this example, E1-2 was changed to E4-1 in equal amount (mol). Target compound E-16(3.26g, 41% yield). Mass spectrum theoretical value [ E-16+ H ]: 939.35, respectively; MALDI-TOF-MS results: m/z: 939.45[ E-16+ H ]. Elemental analysis results: theoretical value: c89.53%, H4.50%, N5.97%. Experimental values: c89.59%, H4.48%, N5.93%.

Synthetic example 11:

synthesis of Compound E-17

This example is substantially the same as synthetic example 7, except that: in this example, E1-2 was changed to E5-1 in equal amount (mol). The target compound E-17(1.69g, 36% yield). Mass spectrum theoretical value [ E-17+ H ]: 555.21, respectively; MALDI-TOF-MS results: m/z: 555.36[ E-17+ H ]. Elemental analysis results: theoretical value: c73.63%, H4.73%, N10.10%, O11.54%. Experimental values: c73.61%, H4.76%, N10.05%, O11.58%.

Synthetic example 12:

synthesis of Compound E-19

This example is substantially the same as synthetic example 7, except that: in this example, E1-2 was changed to E7-1 in equal amount (mol). Target compound E-19(2.95g, 49% yield). Mass spectrum theoretical value [ E-19+ H ]: 711.39, respectively; MALDI-TOF-MS results: m/z: 711.50[ E-19+ H ]. Elemental analysis results: theoretical value: c77.72%, H6.52%, N15.76%. Experimental values: c77.74%, H6.53%, N15.73%.

Synthetic example 13:

synthesis of Compound E-85

This example is substantially the same as synthetic example 7, except that: in this example, E13-2 was changed to E85-2 in equal amount (mol). Target compound E-85(2.45g, 51% yield). Theoretical value of mass spectrum [ E-85+ H ]: 567.25, respectively; MALDI-TOF-MS results: m/z: 567.32[ E-85+ H ]. Elemental analysis results: theoretical value: c84.78%, H5.34%, N9.89%. Experimental values: 84.69 percent of C, 5.36 percent of H and 9.95 percent of N.

Synthesis example 14:

synthesis of Compound E-86

This example is substantially the same as synthetic example 8 except that: in this example, E13-2 was changed to E85-2 in equal amount (mol). Target compound E-86(2.90g, 42% yield). Mass spectrum theoretical value [ E-86+ H ]: 815.32, respectively; MALDI-TOF-MS results: m/z: 815.52[ E-86+ H ]. Elemental analysis results: theoretical value: 88.43 percent of C, 4.70 percent of H and 6.87 percent of N. Experimental values: c88.40%, H4.73%, N6.87%.

Synthetic example 15:

synthesis of Compound E-87

This example is substantially the same as synthetic example 9 except that: in this example, E13-2 was changed to E85-2 in equal amount (mol). The title compound E-86(3.53g, 41% yield). Theoretical value of mass spectrum [ E-87+ H ]: 1015.38, respectively; MALDI-TOF-MS results: m/z: 1015.46[ E-87+ H ]. Elemental analysis results: theoretical value: c89.91%, H4.57%, N5.52%. Experimental values: c89.88%, H4.55%, N5.57%.

Synthetic example 16:

synthesis of Compound E-88

This example is substantially the same as synthetic example 10 except that: in this example, E13-2 was changed to E85-2 in equal amount (mol). Target compound E-88(3.27g, 38% yield). Mass Spectrometry theoretical value [ E-88+ H ]: 1015.38, respectively; MALDI-TOF-MS results: m/z: 1015.49[ E-88+ H ]. Elemental analysis results: theoretical value: c89.91%, H4.57%, N5.52%. Experimental values: c89.94%, H4.58%, N5.48%.

Synthetic example 17:

synthesis of Compound E-181

A500 mL round-bottom flask was charged with E181-2(2.74g, 6mmol), E1-2(4.81g, 19.80mmol), a mixture of toluene (150mL), ethanol (50mL) and deionized water (100mL) as the solvent, and Na was added₂CO₃(6.12g, 57.78mmol) and Pd (PPh)₃)₄(1.08g, 0.933mmol) as a catalyst, heating and refluxing for 36 hours under the protection of nitrogen, filtering after the reaction system is cooled, washing the filter cake with saturated saline and ethanol in sequence, and further processing by a conventional method to obtain a final product E-181(1.97g, 47% yield). Theoretical value of mass spectrum [ E-181+ H]: 697.22, respectively; MALDI-TOF-MS results: m/z: 697.33[ E-181+ H]. Elemental analysis results: theoretical value: c82.73%, H5.21%, N12.06%. Experimental values: c82.38%, H4.92%,N 12.70％。

synthetic example 18:

synthesis of Compound E-313

This example is substantially the same as synthetic example 17 except that: in this case, E181-2 was changed to E313-2 in an equal amount (mol) of the substance. Target compound E-313(3.76g, 38% yield). Mass Spectrometry theoretical value [ E-313+ H ]: 925.39, respectively; MALDI-TOF-MS results: m/z: 925.46[ E-313+ H ]. Elemental analysis results: theoretical value: 85.69% of C, 5.23% of H and 9.08% of N. Experimental values: 85.73% of C, 5.30% of H and 8.97% of N.

Synthesis examples 19 to 48:

the synthesis of specific compounds is detailed in table 1 below.

Table 1:

the technical characteristics and advantages of the invention are shown and verified by the practical application effect of the organic material in the organic electroluminescent device and by testing the performance and performance in the device.

Examples of applications of the compounds of the invention, namely examples of the preparation of OLED devices

The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.

In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.

The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used₂) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.

The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.

The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).

The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives, and the like.

The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds.

The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.

According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.

The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

The electron injection layer in the invention adopts transition metal and the phenanthroline electron injection material in the invention, and the metal includes but is not limited to iron, chromium, niobium, cobalt, manganese, tweezers, copper, zinc, silver, palladium, rhodium, ruthenium, iridium, tungsten, rhenium, platinum, gold and other metals.

The preparation process of the organic electroluminescent device in the embodiment of the invention is as follows:

the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～5×10^-4Pa, carrying out vacuum evaporation on the anode layer film to form HATCN as a hole injection layer, wherein the evaporation rate is 0.05nm/s, and the evaporation film thickness is 5 nm;

NPB is evaporated on the hole injection layer in vacuum to serve as a hole transport layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 30 nm;

the electron blocking layer and the light emitting layer of the device are vacuum evaporated on the hole transport layer, the light emitting layer comprises a main material and a dye material, doping is carried out by adopting a multi-source co-evaporation method, and the speed and the doping concentration are regulated and controlled by a high-low crystal oscillator probe. The evaporation rate of the main body material is adjusted to be 0.1nm/s, the evaporation rate of the dye in the luminescent layer is adjusted to be 1% -5% of the evaporation rate of the main body, the preset doping proportion is further realized, and the total film thickness of the luminescent layer in evaporation is 20-50 nm;

vacuum evaporating a hole blocking layer and an electron transport layer material of the device on the luminescent layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 20-60 nm;

an electron injection layer with a thickness of 5nm was vacuum-evaporated on the Electron Transport Layer (ETL), and an Al layer with a thickness of 150nm was used as the cathode of the device.

Device example 1

The glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10^-5～5×10^-4Pa, carrying out vacuum evaporation on the anode layer film to form HATCN as a hole injection layer, wherein the evaporation rate is 0.05nm/s, and the evaporation film thickness is 5 nm;

NPB is evaporated on the hole injection layer in vacuum to serve as a hole transport layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 30 nm;

the electron blocking layer and the light emitting layer of the device are vacuum evaporated on the hole transport layer, the light emitting layer comprises a main material and a dye material, doping is carried out by adopting a multi-source co-evaporation method, and the speed and the doping concentration are regulated and controlled by a high-low crystal oscillator probe. The evaporation rate of the main body material is adjusted to be 0.1nm/s, the evaporation rate of the dye in the luminescent layer is adjusted to be 1% -5% of the evaporation rate of the main body, the preset doping proportion is further realized, and the total film thickness of the luminescent layer in evaporation is 20-50 nm;

the hole blocking layer and the electron transport layer of the device are vacuum evaporated on the luminescent layer, wherein the materials are Bphen or ET1 in the prior art, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 20-60 nm;

simultaneously evaporating metal Ag and the phenanthroline compound with the specific structure to form an electron injection layer on the Electron Transport Layer (ETL), and realizing in-situ doping by adjusting respective evaporation rates, wherein the ratio of the evaporation rates of the metal Ag and the organic material is 0.5-5% (namely the volume fraction is 0.5-5 vol%), and the total thickness of the electron injection layer is controlled to be 5 nm.

Finally, vacuum evaporation of 150nm Al is continued on the electron injection layer to be used as a cathode of the device.

In this example, 5nm Ag/E-1 (the ratio of the deposition rates of the two is 1%) was used as an electron injection layer, and a 150nm thick Al layer was used as a cathode of the device. So that it has the following structure:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-1(5nm)/Al(150nm)。

device example 2

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-2 from E-1, and the evaporation rate ratio of Ag to E-2 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-2(5nm)/Al(150nm)。

device example 3

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-3 from E-1, and the evaporation rate ratio of Ag to E-3 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-3(5nm)/Al(150nm)。

device example 4

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-4 from E-1, and the evaporation rate ratio of Ag to E-4 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-4(5nm)/Al(150nm)。

device example 5

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-5 from E-1, and the evaporation rate ratio of Ag to E-5 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-5(5nm)/Al(150nm)。

device example 6

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-7 from E-1, and the evaporation rate ratio of Ag to E-7 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-7(5nm)/Al(150nm)。

device example 7

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-13 from E-1, and the evaporation rate ratio of Ag to E-13 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-13(5nm)/Al(150nm)。

device example 8

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-14 from E-1, and the evaporation rate ratio of Ag to E-14 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-14(5nm)/Al(150nm)。

device example 9

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-15 from E-1, and the evaporation rate ratio of Ag to E-15 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-15(5nm)/Al(150nm)。

device example 10

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-16 from E-1, and the evaporation rate ratio of Ag to E-16 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-16(5nm)/Al(150nm)。

device example 11

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-17 from E-1, and the evaporation rate ratio of Ag to E-17 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-17(5nm)/Al(150nm)。

device example 12

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-19 from E-1, and the evaporation rate ratio of Ag to E-19 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-19(5nm)/Al(150nm)。

device example 13

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-85 from E-1, and the evaporation rate ratio of Ag to E-85 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-85(5nm)/Al(150nm)。

device example 14

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-86 from E-1, and the evaporation rate ratio of Ag to E-86 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-86(5nm)/Al(150nm)。

device example 15

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-87 from E-1, and the evaporation rate ratio of Ag to E-87 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-87(5nm)/Al(150nm)。

device example 16

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-88 from E-1, and the evaporation rate ratio of Ag to E-88 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-87(5nm)/Al(150nm)。

device example 17

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-181 from E-1, and the evaporation rate ratio of Ag to E-181 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-181(5nm)/Al(150nm)。

device example 18

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-313 from E-1, and the evaporation rate ratio of Ag to E-313 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-313(5nm)/Al(150nm)。

device example 19

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-337 from E-1, and the evaporation rate ratio of Ag to E-337 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-337(5nm)/Al(150nm)。

device example 20

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-338 from E-1, and the evaporation rate ratio of Ag to E-338 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-338(5nm)/Al(150nm)。

device example 21

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-365 from E-1, and the evaporation rate ratio of Ag to E-365 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-365(5nm)/Al(150nm)。

device example 22

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-367 from E-1, and the evaporation rate ratio of Ag to E-367 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-367(5nm)/Al(150nm)。

device example 23

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-369 from E-1, and the evaporation rate ratio of Ag to E-369 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-369(5nm)/Al(150nm)。

device example 24

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-371 from E-1, and the evaporation rate ratio of Ag to E-371 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-371(5nm)/Al(150nm)。

device example 25

The same preparation method as that of example 1 except that the electron injection layer material was replaced with E-373 from E-1, and the evaporation rate ratio of Ag to E-373 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-373(5nm)/Al(150nm)。

device example 26

The preparation method is the same as that of the embodiment 1, except that the electron injection layer material is replaced by E-383 from E-1, and the evaporation rate ratio of Ag to E-383 is 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-383(5nm)/Al(150nm)。

device example 27

The same preparation method as that of example 1 was repeated, except that the electron injection layer material was replaced with E-391 from E-1, and the evaporation rate ratio of Ag to E-391 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-391(5nm)/Al(150nm)。

device example 28

The same preparation method as that of example 1 was repeated, except that the electron injection layer material was replaced with E-392 from E-1, and the evaporation rate ratio of Ag to E-392 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:E-392(5nm)/Al(150nm)。

comparative device example 1

The same preparation method as that of example 1 except that the electron injecting material was replaced with Ag: E-1 to the prior art compound Cs₂CO₃I.e. the electron injection layer adopts Cs₂CO₃E-1(5nm) wherein Cs₂CO₃The ratio of the evaporation rates of E-1d is 10%.

Comparative device example 2

The same preparation method as in example 1 was used except that the electron injection layer was replaced with the compound LiF (1nm) of the prior art from Ag: E-1(5 nm).

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/LiF(1nm)/Al(150nm)。

Comparative device example 3

The same preparation method as in example 1 was used except that the electron injection layer was replaced with a compound Liq (1nm) of the prior art from Ag: E-1(5 nm).

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Liq(1nm)/Al(150nm)。

Comparative device example 4

The same preparation method as in example 1 was used except that the electron injection layer was replaced with the compound D-1 of the prior art from Ag: E-1(5 nm). The ratio of the evaporation rate of Ag to D-1 was 1%. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:D-1(5nm)/Al(150nm)。

comparative device example 5

The same preparation method as in example 1 was used except that the electron injection layer was replaced with the compound D-2 of the prior art from Ag: E-1(5 nm). The ratio of the evaporation rate of Ag to D-2 was 1%, and the thickness was 5 nm. The device structure is as follows:

ITO/HATCN(5nm)/NPB(30nm)/EBL(10nm)/t-DABNA:α,β-ADN(2％,30nm)/HBL(10nm)/DPPyA(20nm)/Ag:D-2(5nm)/Al(150nm)。

the properties of the organic electroluminescent devices prepared in the above device examples and comparative device examples are shown in table 2 below.

Table 2:

from table 2, it can be seen from examples 5 to 7 and comparative examples 1 to 3 that, under the condition that other materials in the structure of the organic electroluminescent device are the same, the voltage of the OLED device prepared by the compound of the present invention is reduced compared with that of the OLED device prepared by the prior art compound in comparative examples 1 to 3, and at the same time, the efficiency of the device is greatly improved, and the service life of the device is correspondingly improved. It is presumed that in the present invention, when an alkali metal compound is used as an injection material, the alkali metal may migrate or diffuse during thermal evaporation and during operation of the device, resulting in quenching of excitons in the light-emitting layer, resulting in a decrease in efficiency and lifetime. And transition metals such as Ag and the like have strong interaction with phenanthroline organic ligands, so that the migration or diffusion of the metals is inhibited. In addition, the injection performance of the electron injection layer prepared based on the transition metal coordination doping strategy is better, so that the exciton utilization rate and the efficiency and the service life of an OLED device can be improved.

The compound D1 in the prior art adopted in comparative example 4 is 4, 7-diphenyl phenanthroline (Bphen), which is a currently used electron transport material, has a relatively excellent coordination property, and can be used as an efficient electron injection layer in the prior art after being doped with Ag. However, this compound had a molecular weight of only 332.41, and thus had a glass transition temperature of only 62 ℃, and the stability of the film was poor, thus resulting in a relatively low lifetime of comparative example 4.

The prior art compound D2 used in comparative example 5 is a currently commonly used electron transport material, and it can be found by comparison with example 1 using the compound E-1 of the present invention that since E1 is at R of phenanthroline skeleton₁And R₂Methyl is introduced into the position as an electron-donating group, so that the coordination performance of the material is more excellent, and the electron injection performance of the material taking Ag: E1 as an electron injection layer material is obviously superior to that of an electron injection layer consisting of Ag: D2; compared with D2, the device adopting E1 as the organic ligand has lower driving voltage, higher current efficiency and longer service life. Further comparison of comparative example 5 with examples 2 to 6 reveals that R is identical for the backbone groups₁And R₂The stronger the electron donating performance is, the stronger the coordination performance of the corresponding phenanthroline ligand is, and the performance of the electron injection layer prepared according to the method is better, so that the driving voltage of the device is remarkably reduced, the efficiency of the device is improved, and the service life of the device is prolonged. This also reflects the R in the parent nucleus structure of the compounds of the invention₁And R₂The selection of the phenanthroline material and the transition metal have important influence on the performance of the phenanthroline material serving as the electron injection layer.

By comparing 2 groups: examples 1 and 7, and examples 2 and 8, it was found that, for a material containing two phenanthroline skeletons, the electron injection material constructed by adopting the meta-position connection has more excellent efficiency and lifetime than the material adopting the para-position connection, probably because the bonding mode is more favorable for forming coordination with Ag, and excellent electron injection performance is realized.

In conclusion, the multi-o-phenanthroline electron injection material disclosed by the invention has a relatively large molecular weight and has good film stability after being doped with Ag. The coordination performance of the organic light emitting diode can be regulated and controlled by optimizing the design of a molecular structure, and the organic light emitting diode can realize lower work function and excellent electron injection performance when being matched with Ag to serve as an electron injection layer, so that the organic light emitting diode can be applied to OLED devices and can realize higher efficiency and longer service life.

The experimental data show that the organic compound is an organic luminescent functional material with good performance and is expected to be popularized and applied commercially.

Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims. It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.