CN113410401B

CN113410401B - Organic electroluminescent device comprising deep LUMO hole injection material and aromatic amine derivative

Info

Publication number: CN113410401B
Application number: CN202010180701.3A
Authority: CN
Inventors: 赵春亮; 王峥; 张少博; 毕欣; 夏传军; 邝志远
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2020-03-16
Filing date: 2020-03-16
Publication date: 2023-09-05
Anticipated expiration: 2040-03-16
Also published as: CN113410401A

Abstract

An organic electroluminescent device comprising a hole injection material of deep LUMO and an aromatic amine derivative is disclosed. The organic electroluminescent device combines pyrene substituted by ortho-deuterated alkyl aromatic amine structure as a luminescent material and a specific hole injection layer material, so that the service life and power efficiency of the organic electroluminescent device can be obviously improved.

Description

Organic electroluminescent device comprising deep LUMO hole injection material and aromatic amine derivative

Technical Field

The present invention relates to an organic electronic device, such as an organic electroluminescent device. And more particularly, to an organic electroluminescent device comprising an aromatic amine derivative and an organic hole injection material comprising a deep LUMO.

Background

Organic electronic devices include, but are not limited to, the following: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLEDs), organic photovoltaic devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes and organic electroluminescent devices.

In 1987, tang and Van Slyke of Isomandah reported a double-layered organic electroluminescent device comprising an arylamine hole transport layer and a tris-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light emitting layer (Applied Physics Letters,1987,51 (12): 913-915). Once biased into the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). Most advanced OLEDs may include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light emitting layers between the cathode and anode. Because OLEDs are self-emitting solid state devices, they offer great potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications, such as in flexible substrate fabrication.

OLEDs can be divided into three different types according to their light emission mechanism. The OLED of the Tang and van Slyke invention is a fluorescent OLED. It uses only singlet light emission. The triplet states generated in the device are wasted through non-radiative decay channels. Thus, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation prevents commercialization of OLEDs. In 1997, forrest and Thompson reported phosphorescent OLEDs using triplet emission from heavy metals containing complexes as emitters. Thus, both singlet and triplet states can be harvested, achieving a 100% IQE. Because of its high efficiency, the discovery and development of phosphorescent OLEDs has contributed directly to the commercialization of Active Matrix OLEDs (AMOLEDs). Recently, adachi achieved high efficiency by Thermally Activated Delayed Fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, making it possible for excitons to return from the triplet state to the singlet state. In TADF devices, triplet excitons can generate singlet excitons by reverse intersystem crossing, resulting in high IQE.

OLEDs can also be classified into small molecule and polymeric OLEDs depending on the form of the materials used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of the small molecules can be large as long as they have a precise structure. Dendrimers with a defined structure are considered small molecules. Polymeric OLEDs include conjugated polymers and non-conjugated polymers having pendant luminescent groups. Small molecule OLEDs can become polymeric OLEDs if post-polymerization occurs during fabrication.

Various methods of OLED fabrication exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymeric OLEDs are manufactured by solution processes such as spin coating, inkjet printing and nozzle printing. Small molecule OLEDs can also be fabricated by solution processes if the material can be dissolved or dispersed in a solvent.

The hole injection layer is an important functional layer affecting the performance of the organic electroluminescent device, and the selection and collocation of materials seriously affect the driving voltage, efficiency and service life of the organic electroluminescent device. It is commercially desirable to obtain an organic electroluminescent device with characteristics of low driving voltage, high efficiency, long service life, etc., and it is important to select a suitable combination of a hole injection layer material and a fluorescent light emitting layer material to achieve the above object.

The organic light emitting display device uses a hole injection layer and an electron injection layer to facilitate charge injection. Wherein the hole injection layer is a functional layer formed of a single material or more than one material. Single material methods typically utilize shallow HOMO materials such as triarylamine materials or deep LUMO materials, while more than one material is formed by doping a P-type, deep LUMO material into a hole transporting material. Through researches, the deuterated alkyl substituted pyrene is used as a blue light luminescent material and a deep LUMO material or a P-doped hole transport material, so that a blue light device with high efficiency and long service life can be achieved. It is well known that blue light performance is the weakest link in an OLED, so it is important to the industry to improve blue device performance.

Compounds of the general formula are disclosed in U.S. Pat. No. 3,182,1A 1Wherein Ra is a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, and specific examples disclosed therein include:however, in the disclosed structure of this application, the substituent group of the alkyl group is not subjected to research on substitution of deuterium atoms, and is all alkyl groups substituted by hydrogen atoms, which do not pay attention to the special advantage of deuterated alkyl groups in the service life of the device, and do not explore the effect of the device caused by the use of deuterated alkyl groups in combination with a special organic hole injection layer material.

CN109608342A discloses a compound of the general formulaAnd a series of alkyl groups, wherein Ar ₁ 、Ar ₂ 、R ₁₀₁ And R is ₁₀₂ At least one of the alkyl groups disclosed above, and at least one H atom of these alkyl groups is replaced by a D atom. However, the inorganic hole injection layer is used in the research of the device, and the effect of the device caused by the cooperation of the inorganic hole injection layer and the special organic hole injection layer material is not explored.

Numerous pyrene-based fluorescent materials with aromatic amine structures are disclosed in the prior art, but related fluorescent technologies still need further development to obtain higher device efficiency, longer device lifetime, and the like. The inventor has intensively studied and found that when the aromatic amine substituted pyrene compound is applied to an organic electroluminescent device to be used as a luminescent material, the novel material combination can obviously improve the performance of the organic electroluminescent device, such as obviously prolonging the service life of the device and improving the power efficiency of the device, in combination with the use of a specific hole injection layer material.

Disclosure of Invention

The present invention aims to provide a novel organic electroluminescent device comprising an aromatic amine derivative and an organic hole injection material, which can significantly improve the lifetime and power efficiency of the organic electroluminescent device by combining pyrene substituted with an ortho-deuterated alkylarylamine structure as a light emitting material and a specific hole injection layer material, to solve at least part of the above problems.

According to an embodiment of the present invention, an organic electroluminescent device is disclosed, comprising:

an anode is provided with a cathode,

a cathode electrode, which is arranged on the surface of the cathode,

and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises at least a first organic layer and a second organic layer;

wherein the organic layer comprises at least one organic hole injection layer material; wherein the organic hole injection layer material has a LUMO less than-4.81 eV;

wherein the organic layer one contains a compound represented by formula 1:

wherein, in the formula 1,

R ₁ to R ₁₀ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, phosphino, sulfinyl, sulfonyl, and combinations thereof;

And, substituent R ₁ To R ₁₀ At least one of which has the structure of formula 2:

wherein, in the formula 2,

* Represents a position where the substituent having the structure represented by formula 2 is attached to formula 1;

X ₁ to X ₅ Is selected identically or differently at each occurrence from C, CR _a1 Or N, X ₆ To X ₁₀ Is selected identically or differently at each occurrence from CR _a2 Or N; x is X ₁ To X ₅ At least one of which is selected from C and is connected with L;

l is, identically or differently, selected at each occurrence from a single bond, a substituted or unsubstituted alkylene group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having from 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having from 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having from 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having from 3 to 30 carbon atoms;

m is selected identically or differently on each occurrence from 1, 2 or 3;

n is selected identically or differently on each occurrence from 0, 1 or 2; when n is 2, two R may be the same or different;

and m+n=3;

therein, R, R _a1 And R is _a2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, phosphino, sulfinyl, sulfonyl, and combinations thereof;

Adjacent substituents R _a2 Can optionally be linked to form a ring.

According to another embodiment of the present invention, an electronic device is also disclosed, which includes the organic electroluminescent device described in the foregoing embodiment.

The invention provides a novel organic electroluminescent device containing aromatic amine derivatives and organic hole injection materials, wherein the organic electroluminescent device combines pyrene substituted by ortho-deuterated alkyl aromatic amine structure as a luminescent material and a specific hole injection layer material, and the novel material combination can provide better device performance, for example, the power efficiency and the service life of the organic electroluminescent device can be obviously improved.

Drawings

Fig. 1 is a schematic diagram of an organic light emitting device that may contain a combination of materials disclosed herein.

Fig. 2 is a schematic view of another organic light emitting device that may contain a combination of materials disclosed herein.

Detailed Description

OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically illustrates, without limitation, an organic light-emitting device 100. The drawings are not necessarily to scale, and some of the layer structures in the drawings may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the layers described. The nature and function of the layers and exemplary materials are described in more detail in U.S. patent US7,279,704B2, columns 6-10, the entire contents of which are incorporated herein by reference.

There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F in a 50:1 molar ratio ₄ m-MTDATA of TCNQ as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1 as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose cathodesIncluding a composite cathode having a thin layer of metal, such as Mg: ag, with an overlying transparent, conductive, sputter deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

The above-described hierarchical structure is provided by way of non-limiting example. The function of the OLED may be achieved by combining the various layers described above, or some of the layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sublayers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.

In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.

The OLED also requires an encapsulation layer, such as the organic light emitting device 200 shown schematically and without limitation in fig. 2, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to prevent harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film packages are described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.

Devices manufactured according to embodiments of the present invention may be incorporated into a variety of consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, heads-up displays, displays that are fully or partially transparent, flexible displays, smart phones, tablet computers, tablet phones, wearable devices, smart watches, laptops, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and taillights.

The materials and structures described herein may also be used in other organic electronic devices as listed above.

As used herein, "top" means furthest from the substrate and "bottom" means closest to the substrate. In the case where the first layer is described as being "disposed" on "the second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed on" an anode even though various organic layers are present between the cathode and the anode.

As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium in the form of a solution or suspension.

A ligand may be referred to as "photosensitive" when it is believed that the ligand directly contributes to the photosensitive properties of the emissive material. When it is believed that the ligand does not contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary," but ancillary ligands may alter the properties of the photosensitive ligand.

It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by spin statistics that delay fluorescence by more than 25%. Delayed fluorescence can be generally classified into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. The P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).

On the other hand, the E-type delayed fluorescence does not depend on the collision of two triplet states, but on the transition between the triplet states and the singlet excited state. Compounds capable of generating E-type delayed fluorescence need to have very small mono-triplet gaps in order for the conversion between the energy states. The thermal energy may activate a transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). A significant feature of TADF is that the delay component increases with increasing temperature. The fraction of backfill singlet excited states may reach 75% if the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet states. The total singlet fraction may be 100%, well in excess of 25% of the spin statistics of the electrically generated excitons.

Type E delayed fluorescence features can be found in excitation complex systems or in single compounds. Without being bound by theory, it is believed that E-delayed fluorescence requires a luminescent material with a small mono-triplet energy gap (Δe _S-T ). Organic non-metal containing donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is typically characterized as donor-acceptor Charge Transfer (CT) type emission. The spatial separation of HOMO from LUMO in these donor-acceptor compounds generally results in a small Δe _S-T . These states may include CT states. Typically, donor-acceptor luminescent materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., an N-containing six-membered aromatic ring).

Definition of terms for substituents

Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.

Alkyl-includes straight and branched alkyl groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. In addition, the alkyl group may be optionally substituted. The carbon in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferred.

Cycloalkyl-as used herein, includes cyclic alkyl. Preferred cycloalkyl groups are cycloalkyl groups containing 4 to 10 ring carbon atoms, including cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. In addition, cycloalkyl groups may be optionally substituted. The carbon in the ring may be substituted with other heteroatoms.

Alkenyl-as used herein, covers both straight chain and branched alkene groups. Preferred alkenyl groups are alkenyl groups containing 2 to 15 carbon atoms. Examples of alkenyl groups include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, 1-methylvinyl, styryl, 2-diphenylvinyl, 1-methallyl, 1-dimethylallyl, 2-methallyl, 1-phenylallyl, 2-phenylallyl, 3-diphenylallyl, 1, 2-dimethylallyl, 1-phenyl-1-butenyl and 3-phenyl-1-butenyl. In addition, alkenyl groups may be optionally substituted.

Alkynyl-as used herein, covers both straight and branched chain alkynyl groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, alkynyl groups may be optionally substituted.

Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methylbiphenyl-yl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, allTrimethylphenyl and m-tetrabiphenyl.

Heterocyclyl or heterocycle-as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.

Heteroaryl-as used herein, non-fused and fused heteroaromatic groups are contemplated that may contain 1 to 5 heteroatoms. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, furodipyridine, benzothiophene, thienodipyridine, benzoselenophene, selenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-aza-boron, 1, 3-aza-boron, 1-aza-boron-4-aza, boron-doped compounds, and the like. In addition, heteroaryl groups may be optionally substituted.

Alkoxy-is represented by-O-alkyl. Examples of alkyl groups and preferred examples are the same as described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy groups. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.

Aryloxy-is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. Examples of the aryloxy group having 6 to 40 carbon atoms include phenoxy and diphenoxy.

Aralkyl-as used herein, an alkyl group having an aryl substituent. In addition, aralkyl groups may be optionally substituted. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthyl-ethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthyl-ethyl, 2- β -naphthyl-ethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, cyano, o-cyanobenzyl, o-chlorobenzyl, 1-chlorophenyl and 1-isopropyl. Among the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl.

The term "aza" in aza-dibenzofurans, aza-dibenzothiophenes and the like means that one or more C-H groups in the corresponding aromatic fragment are replaced by nitrogen atoms. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives will be readily apparent to those of ordinary skill in the art, and all such analogs are intended to be included in the terms described herein.

In the present disclosure, when any one of the terms from the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted silyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, refers to any one or more groups selected from alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, silyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups that may be substituted with one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted silyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylate, ester, cyano, isocyano, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof.

It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered equivalent.

In the compounds mentioned in this disclosure, the hydrogen atoms may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because of their enhanced efficiency and stability of the device.

In the compounds mentioned in this disclosure, multiple substitution is meant to encompass double substitution up to the maximum available substitution range. When a substituent in a compound mentioned in this disclosure means multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), it means that the substituent may be present at a plurality of available substitution positions on its linking structure, and the substituent present at each of the plurality of available substitution positions may be of the same structure or of different structures.

The Hammett substituent value of the electron withdrawing group is more than or equal to 0.05, the electron withdrawing capability is strong, the LUMO energy level of the compound can be obviously reduced, and the effect of improving the charge mobility is achieved. The Hammett substituent constant value includes a Hammett substituent para-constant and/or meta-constant, and may be a preferable selection group of the present invention as long as one of the para-constant and meta-constant satisfies 0.05 or more.

The values for HOMO (highest occupied orbital) and LUMO (lowest unoccupied orbital) referred to herein were calculated using Gaussian 09 software, the B3LYP method, basis set 6-311g (d). All "HOMO" and "LUMO" energy levels herein take their calculated actual values. For example, the LUMO level of the compound HATCN calculated by this method is-4.81 eV.

In the compounds mentioned in this disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless explicitly defined, for example, adjacent substituents can optionally be linked to form a ring. In the compounds mentioned in this disclosure, adjacent substituents can optionally be linked to form a ring, both in the case where adjacent substituents can be linked to form a ring and in the case where adjacent substituents are not linked to form a ring. Where adjacent substituents can optionally be joined to form a ring, the ring formed may be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to further distant carbon atoms. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

The expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

furthermore, the expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that, in the case where one of the two substituents bonded to carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:

an anode is provided with a cathode,

a cathode electrode, which is arranged on the surface of the cathode,

Wherein the organic layer one contains a compound represented by formula 1:

wherein, in the formula 1,

Wherein, in the formula 2,

m is selected identically or differently on each occurrence from 1, 2 or 3;

and m+n=3;

R、R _a1 and R is _a2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, phosphino, sulfinyl, sulfonyl, and combinations thereof;

Adjacent substituents R _a2 Can optionally be linked to form a ring.

According to an embodiment of the present invention, wherein the substituent having formula 2 further has a structure represented by formula 3:

wherein, in the formula 3,

* Represents a position where the substituent having the structure represented by formula 3 is attached to formula 1;

X ₁ to X ₄ Is selected identically or differently at each occurrence from CR _a1 Or N; x is X ₆ To X ₁₀ Is selected identically or differently at each occurrence from CR _a2 Or N;

m is selected identically or differently on each occurrence from 1, 2 or 3;

and m+n=3;

Adjacent substituents R _a2 Can optionally be linked to form a ring. .

According to an embodiment of the present invention, wherein the substituent having formula 2 further has a structure represented by formula 4, formula 5 or formula 6:

wherein in formula 4, formula 5 or formula 6

Ar is selected identically or differently on each occurrence from the group consisting of: substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms;

x is selected identically or differently at each occurrence from 0, 1, 2 or 3;

y is selected identically or differently at each occurrence from 0, 1, 2, 3 or 4;

X ₆ to X ₁₀ Is selected identically or differently at each occurrence from CR _a2 Or N;

m is selected identically or differently on each occurrence from 1, 2 or 3;

And m+n=3;

R、R _a1 and R is _a2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aralkyl having 1 to 20 carbon atomsAn alkoxy group of a child, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

adjacent substituents R _a2 Can optionally be linked to form a ring.

According to one embodiment of the present invention, wherein the substituent R in formula 1 ₁ To R ₁₀ At least two of which have the structure of formula 2.

According to one embodiment of the present invention, wherein the substituent R in formula 1 ₁ -R ₁₀ Two of which have the structure of formula 2.

According to one embodiment of the present invention, wherein the substituent R in formula 1 ₁ And R is ₆ Has a structure represented by formula 2, and R ₁ And R is ₆ Are the same or different; r is R ₂ To R ₅ ，R ₇ To R ₁₀ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, Carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphine groups, and combinations thereof.

According to one embodiment of the present invention, wherein the substituent R in formula 1 ₁ And R is ₆ Has a structure represented by formula 2, and R ₁ And R is ₆ Are the same or different; r is R ₂ ，R ₄ -R ₅ ，R ₇ And R is ₉ -R ₁₀ Is hydrogen, R ₃ And R is ₈ And is selected identically or differently on each occurrence from hydrogen, substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms.

According to one embodiment of the present invention, wherein X in formula 2 ₁ To X ₅ Is selected identically or differently at each occurrence from CR _a1 、X ₆ To X ₁₀ Is selected identically or differently at each occurrence from CR _a2 Wherein R is _a1 、R _a2 And are selected, identically or differently, at each occurrence from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 12 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 12 carbon atoms, substituted or unsubstituted amine groups having 0 to 6 carbon atoms, cyano groups, isocyano groups, and combinations thereof.

According to one embodiment of the invention, wherein adjacent substituents R _a2 Are not connected to form a ring.

According to one embodiment of the invention, wherein L is selected identically or differently on each occurrence from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms.

According to one embodiment of the invention, wherein L is selected identically or differently on each occurrence from a single bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 6 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 6 carbon atoms.

According to one embodiment of the invention, wherein L is selected identically or differently at each occurrence from a single bond, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene.

According to one embodiment of the invention, wherein Ar is selected identically or differently on each occurrence from a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

According to one embodiment of the invention, ar is selected identically or differently on each occurrence from phenyl or biphenyl.

According to one embodiment of the invention, wherein R _a1 And R is _a2 And are selected, identically or differently, at each occurrence from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 12 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 12 carbon atoms, substituted or unsubstituted amine groups having 0 to 6 carbon atoms, cyano groups, isocyano groups, and combinations thereof.

According to one embodiment of the invention, wherein R _a1 And R is _a2 And is selected, identically or differently, at each occurrence, from: hydrogen, deuterium, fluorine, cyano, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, 4-dimethylcyclohexyl, phenyl, biphenyl.

According to one embodiment of the invention, wherein R is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, cyclopropyl, deuterated cyclopropyl, n-butyl, deuterated n-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, cyclohexyl, deuterated cyclohexyl, 4-dimethylcyclohexyl, deuterated 4, 4-dimethylcyclohexyl, phenyl, biphenyl, and combinations thereof.

According to an embodiment of the present invention, wherein the compound represented by formula 1 is selected from the group consisting of compound 1-1 to compound 1-37, compound 2-1 to compound 2-40, compound 3-1 to compound 3-72, compound 4-1 to compound 4-16, compound 5-1 to compound 5-24, compound 6-1 to compound 6-24, compound 7-1 to compound 7-72, and compound 8-1 to compound 8-24:

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according to an embodiment of the present invention, the organic hole injection material has a LUMO of-4.90 eV or less.

According to an embodiment of the present invention, the organic hole injection material has a LUMO of-5.00 eV or less.

According to one embodiment of the invention, wherein the organic hole injection material is selected from compounds having the structure of formula 7 or having the structure of formula 8:

wherein in formula 8, ring B represents a substituted or unsubstituted carbocycle having 3 to 30 ring atoms, or a substituted or unsubstituted heterocycle having 3 to 30 ring atoms;

wherein q is selected from 0,1,2,3 or 4;

wherein in formula 7 and formula 8, X is selected identically or differently at each occurrence from CR ¹¹ R ¹² ,NR ¹³ O, S or Se;

wherein in formula 7, U is selected identically or differently at each occurrence from CR ¹⁴ Or N; y is selected identically or differently at each occurrence from CR ¹⁵ Or N; z is, identically or differently, selected at each occurrence from NR ¹⁶ O, S or Se;

R ¹¹ ，R ¹² ，R ¹³ ，R ¹⁴ ，R ¹⁵ ，R ¹⁶ and is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ A boron alkyl group, a sulfinyl group, a sulfonyl group, a phosphinoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

adjacent substituents R ¹¹ ，R ¹² And R is ¹³ Can optionally be linked to form a ring;

adjacent substituents R ¹⁴ ，R ¹⁵ And R is ¹⁶ Can optionally be linked to form a ring;

according to one embodiment of the invention, wherein said R ¹¹ ，R ¹² And R is ¹³ Is a group having at least one electron withdrawing group.

According to one embodiment of the invention, wherein said R ¹⁴ ，R ¹⁵ And R is ¹⁶ Is a group having at least one electron withdrawing group.

According to one embodiment of the invention, wherein X is CR ¹¹ R ¹² The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is ¹¹ And R is ¹² And is selected identically or differently on each occurrence from groups having at least one electron withdrawing group.

According to one embodiment of the invention, U is CR ¹⁴ The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is selected identically or differently on each occurrence from groups having at least one electron withdrawing group.

According to one embodiment of the invention, wherein R ¹⁴ The same or different at each occurrence is selected from the group consisting of substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms; preferably, wherein the aryl and heteroaryl groups are substituted with at least one electron withdrawing group.

According to one embodiment of the invention, wherein the Hammett constant of the electron withdrawing group is ≡0.05.

According to one embodiment of the invention, wherein the Hammett constant of the electron withdrawing group is ≡0.3.

According to one embodiment of the invention, wherein the Hammett constant of the electron withdrawing group is ≡0.5.

The Hammett substituent value of the electron withdrawing group is more than or equal to 0.05, the electron withdrawing capability is strong, the LUMO energy level of the compound can be obviously reduced, and the effect of improving the charge mobility is achieved.

The Hammett substituent constant value includes a Hammett substituent para-constant and/or meta-constant, and may be a preferable selection group of the present invention as long as one of the para-constant and meta-constant satisfies 0.05 or more.

According to one embodiment of the invention, wherein the electron withdrawing group is selected from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Borane, sulfinyl, sulfonyl, phosphinoxy, azaaromatic ring groups, or groups substituted by halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Any of the following substituted with one or more of borane, sulfinyl, sulfonyl, phosphinoxy, azaaryl groups: alkyl groups having 1-20 carbon atoms, cycloalkyl groups having 3-20 ring carbon atoms, heteroalkyl groups having 1-20 carbon atoms, aralkyl groups having 7-30 carbon atoms, alkoxy groups having 1-20 carbon atoms, aryloxy groups having 6-30 carbon atoms, alkenyl groups having 2-20 carbon atoms, alkynyl groups having 2-20 carbon atoms, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, alkylsilyl groups having 3-20 carbon atoms, arylsilyl groups having 6-20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein the electron withdrawing group is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pyrimidinyl, triazinyl, and combinations thereof.

According to one embodiment of the invention, wherein X is selected identically or differently on each occurrence from the group consisting of the following structures:

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wherein R is ¹ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ A boron alkyl group, a sulfinyl group, a sulfonyl group, a phosphinoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

Wherein V and W are selected identically or differently at each occurrence from the group consisting of CR _v R _w ，NR _v O, S and Se;

wherein Ar' is, identically or differently, selected at each occurrence from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;

wherein A, R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _i ，R _v And R is _w And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ A borane group, a sulfinyl group, a sulfonyl group, a phosphonoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atomsSubstituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

Wherein A is a group having an electron withdrawing group, and for any of the structures, when R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _i ，R _v And R is _w At least one of which is a group having an electron withdrawing group; preferably, the group having an electron withdrawing group is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl or triazinyl, and combinations thereof.

In this embodiment, "×" indicates the position of the X group attached to formula 7 or formula 8.

According to one embodiment of the invention, wherein R ¹ And is selected identically or differently on each occurrence from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl or triazinyl, and combinations thereof.

According to one embodiment of the invention, wherein X is selected identically or differently on each occurrence from A1 or A2.

According to one embodiment of the invention, wherein R ¹¹ ，R ¹² ，R ¹³ ，R ¹⁴ ，R ¹⁵ ，R ¹⁶ And R is ¹ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, methyl, isopropyl, NO ₂ ，SO ₂ CH ₃ ，SCF ₃ ，C ₂ F ₅ ，OC ₂ F ₅ ，OCH ₃ Diphenylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2, 6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, dimethylphosphinyloxy, diphenylphosphinyloxy, F, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ CN, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, pyridyl, diphenylborane, oxaborolidinyl, vinyl substituted with one or more of CN and CF3, vinyl substituted with CN or CF ₃ Is a substituted ethynyl group, is F, CN and CF ₃ Phenyl or biphenyl groups, and combinations thereof.

According to one embodiment of the invention, wherein the compound having the structures of formula 7 and formula 8 is selected from the group consisting of the following compounds HI-1 to HI-48:

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in this example, the LUMO levels of the compounds HI-1 to HI-48 and HATCN were calculated by DFT theory, specifically by Gaussian 09 software, B3LYP method, 6-311g (d) base, and the calculated results were all less than-4.81 ev, and the specific LUMO levels are shown in the following table:

TABLE 1 LUMO energy levels of Compounds HI-1 to HI-48

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In this example, "less than-4.81 eV" means that the actual value of the calculation result is less than-4.81 eV, and since these LUMO values are negative, the value is less than-4.81 eV, which means that the absolute value is greater than 4.81, for example, the calculated LUMO level of HI-1 is-4.92 eV, the value is less than-4.81 eV, the absolute value is 4.92, and the absolute value is greater than 4.81.

According to one embodiment of the present invention, wherein the first organic layer in the organic electroluminescent device is a light emitting layer, wherein the compound having formula 1 is an organic light emitting material.

According to one embodiment of the invention, the light emitting layer further comprises a host material.

According to one embodiment of the invention, wherein the host material comprises a compound having formula 9:

wherein R is _d1 To R _d8 Each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstitutedSubstituted or unsubstituted aralkyl having from 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having from 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having from 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having from 2 to 20 carbon atoms, substituted or unsubstituted aryl having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having from 3 to 30 carbon atoms, substituted or unsubstituted silyl having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilane having from 6 to 20 carbon atoms, substituted or unsubstituted amine having from 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

R _d9 And R is _d10 Each independently selected from a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 3 to 30 carbon atoms.

According to one embodiment of the present invention, the second organic layer is a hole injection layer, and the hole injection layer is formed by the hole injection layer material alone.

According to one embodiment of the present invention, the second organic layer is a hole injection layer or a hole transport layer.

According to one embodiment of the present invention, wherein the hole injection layer or hole transport layer further comprises at least one hole transport material comprising a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylenevinylene compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the molar doping ratio of the hole injection layer material to the hole transport material is 10000:1 to 1:10000.

according to another embodiment of the present invention, an electronic device is also disclosed, which includes the organic electroluminescent device according to any of the foregoing embodiments.

Combined with other materials

The materials described herein for specific layers in an organic electroluminescent device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application 2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

Materials described herein as useful for specific layers in an organic electroluminescent device may be used in combination with a variety of other materials present in the device. For example, the luminescent dopants disclosed herein may be used in combination with a variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. 2015/0349273A1, paragraphs 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

In the examples of material synthesis, all reactions were carried out under nitrogen protection, unless otherwise indicated. All reaction solvents were anhydrous and used as received from commercial sources. The synthetic products were subjected to structural confirmation and characterization testing using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph, liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai's optical technique fluorescence spectrophotometer, wuhan Koste's electrochemical workstation, anhui Bei Yi g sublimator, etc.), in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, a vapor deposition machine manufactured by Angstrom Engineering, an optical test system manufactured by Frieda, st. John's, an ellipsometer manufactured by Beijing, etc.), in a manner well known to those skilled in the art. Since those skilled in the art are aware of the relevant contents of the device usage and the testing method, and can obtain the intrinsic data of the sample certainly and uninfluenced, the relevant contents are not further described in this patent.

Material synthesis examples:

the preparation method of the compound of the present invention is not limited, and is typically, but not limited to, exemplified by the following compounds, the synthetic routes and preparation methods thereof are as follows:

synthesis example 1: synthesis of Compound 4-1

Step 1:

5-bromo-2-methylaniline (20.0 g,107.5 mmol), phenylboronic acid (15.7 g,129.2 mmol), tetrakis (triphenylphosphine) palladium (6.2 g,5.38 mmol) and potassium carbonate (37.0 g,268.8 mmol) were added sequentially to a dry 1000mL two-necked flask under nitrogen protection, after three nitrogen substitutions, toluene (240 mL), absolute ethanol (95 mL) and water (95 mL) were added and the flask was purged with nitrogen for 5min, heated to 90℃and the reaction was allowed to complete until the starting material was purified by column chromatography to give 4-methyl- [1,1' -biphenyl ] -3-amine (13.5 g,73.7mmol, 68.5% yield as a white solid).

Step 2:

under the protection of nitrogen, 4-methyl- [1,1' -biphenyl ] -3-amine (10.5 g,57.3 mmol) is added into a dry 1000mL two-neck flask, 100mL tetrahydrofuran is added for dissolution, 80mL hydrochloric acid (6M) is added, then stirring and cooling are carried out in an ice bath, sodium nitrite is prepared into saturated solution drops, the saturated solution drops into a reaction system, and stirring and reacting are carried out in the ice bath for 30min. Then an aqueous solution of potassium iodide was added and stirred overnight at room temperature. After the reaction was stopped, most of the tetrahydrofuran was removed by spin-drying under reduced pressure, the reaction mixture was extracted three times with methylene chloride and saturated brine. The organic phases were combined and purified by column chromatography to give 3-iodo-4-methyl-1, 1' -biphenyl (15 g,51.0mmol, 89% yield) as a white solid.

Step 3:

to a dry 500mL three-necked flask under nitrogen protection was added the compound 4-methyl- [1,1 '-biphenyl ] -3-amine (7.47 g,40.8 mmol), 3-iodo-4-methyl-1, 1' -biphenyl (8 g,27.2 mmol), tris (dibenzylideneacetone) dipalladium (627 mg,1.36 mmol), BINAP (1.69 g,2.72 mmol) and sodium t-butoxide (5.23 g,54.4 mmol) in place of nitrogen three times, and then 200mL of xylene was added, nitrogen was introduced into the reaction system, and the reaction was heated to 100℃until the raw materials reacted completely with petroleum ether: column chromatography purification with dichloromethane=5:1 as eluent afforded bis (4-methyl- [1,1' -biphenyl ] -3-yl) amine (5.9 g,16.9mmol, 62.1%) as a white solid.

Step 4:

the compound bis (4-methyl- [1,1' -biphenyl) was charged into a dry 100mL three-necked flask under nitrogen protection]-3-yl) amine (5.9 g,16.9 mmol), 20mL deuterated DMSO, potassium tert-butoxide (2.24 g,20 mmol) were added, heated to 80℃and reacted for 4 hours, cooled to room temperature, added with water and extracted with DCM, the organic phase was dried by spinning, and column chromatography was performed to obtain the intermediate bis (4-methyl (d) ₃ ) - [1,1' -biphenylyl ]]-3-yl) amine (5.5 g,15.7mmol, 92.9% yield).

Step 5:

pd (OAc) ₂ (52mg,0.23mmol),tBu ₃ PH ⁺ BF4 ^- (134 mg,0.46 mmol) was added to a 250mL two-necked flask, and xylene (100 mL) was added. N is introduced into the solution ₂ For 20 minutes until the color no longer changes1, 6-dibromopyrene (2.77 g,7.68 mmol) was added sequentially, as was bis (4-methyl (d 3) - [1,1' -biphenyl)]-3-yl) amine (5.5 g,15.7 mmol), sodium t-butoxide (3.69 g,38.4 mmol). Continuing to feed N ₂ For 10 minutes, the system was heated to 90 ℃ until the starting materials were completely reacted. At the end of the reaction, the product compound 4-1 (2.4 g,2.68mmol, 34.9% yield) was isolated by column chromatography. The product was identified as the target product and had a molecular weight of 909.

Synthesis example 2: synthesis of Compound 8-1

Step 1:

to a dry 500mL three-necked flask under nitrogen protection was added the compound 4-methyl- [1,1' -biphenyl ] -3-amine (18.3 g,100 mmol), 1-bromo-3-methylbenzene (13.68 g,80 mmol), tris (dibenzylideneacetone) dipalladium (1.2 g,2.72 mmol), BINAP (3.4 g,5.4 mmol) and sodium tert-butoxide (19.6 g,200 mmol) in place of nitrogen three times, and after adding 500mL of xylene, introducing nitrogen into the reaction system, heating to 100℃until the raw materials reacted completely to give crude petroleum ether: toluene=5:1 as eluent to give 4-methyl-N- (m-methylphenyl) - [1,1' -biphenyl ] -3-amine (18 g,65.9mmol, 62.1% yield) as a colorless liquid.

Step 2:

the compound 4-methyl-N- (m-methylphenyl) - [1,1' -biphenyl was charged to a dry 100mL three-necked flask under nitrogen protection ]-3-amine (12 g,44 mmol), 50mL deuterated DMSO, potassium tert-butoxide (7 g,62.5 mmol) were added, heated to 110deg.C and reacted for 12 hours, cooled to room temperature, added with water and extracted with DCM, the organic phase was dried by spin-drying and separated by column chromatography to obtain intermediate 4-methyl (d) ₃ ) -N- (m-methyl (d) ₃ ) Phenyl) - [1,1' -biphenyl ]]3-amine (10 g,36.6 mmol).

Step 3:

pd (OAc) ₂ (60mg,0.25mmol),t-Bu ₃ PH·BF ₄ (145 mg,0.5 mmol) was placed in a 100mL three-necked flask, and xylene (50 mL) was added. N is introduced into the solution ₂ After 20 minutes until the color no longer changes, 1, 6-dibromopyrene (1.8 g,5 mmol), 4-methyl (d ₃ ) -N- (m-methyl (d) ₃ ) Phenyl) - [1,1' -biphenyl ]]3-amine (3.82 g,14 mmol), sodium t-butoxide (2.0 g,20 mmol). Continuing to feed N ₂ For 10 minutes, the system was heated to 80 ℃ until the starting materials were completely reacted. After the completion of the reaction, the product compound 8-1 (1.9 g, yield 38.9%) was obtained by separation using column chromatography. The product was identified as the target product and had a molecular weight of 756.

Synthetic comparative example 1: synthesis of comparative Compound A

Step 1:

pd (OAc) ₂ (52mg,0.23mmol)，tBu ₃ PH ⁺ BF ₄ ^- (134 mg,0.46 mmol) was placed in a 250mL two-necked flask and xylene (100 mL) was added. N is introduced into the solution ₂ After 20 minutes until the color no longer changes, 1, 6-dibromopyrene (2.77 g,7.68 mmol) was added, bis (4-methyl- [1,1' -biphenyl) ]3-yl) amine (5.9 g,16.9 mmol), sodium t-butoxide (3.69 g,38.4 mmol). Continuing to feed N ₂ For 10 minutes, the system was heated to 90 ℃ until the starting materials were completely reacted. After the reaction was completed, the sample was dried and separated by column chromatography to give the product comparative compound a (2.4 g,2.68mmol, yield 34.9%). The product was identified as the target product and had a molecular weight of 896.

Synthetic comparative example 2: synthesis of comparative Compound B

Step 1:

pd (OAc) ₂ (60mg,0.25mmol),t-Bu ₃ PH·BF ₄ (145 mg,0.5 mmol) was placed in a 100mL three-necked flask, and xylene (50 mL) was added. N is introduced into the solution ₂ 1, 6-dibromopyrene (1.8 g,5 mmol) was added sequentially for 20 minutes until the color was no longer changed, 4-methyl-N- (m-methylphenyl) - [1,1' -biphenyl ]]3-amine (3.82 g,14 mmol), sodium t-butoxide (2.0 g,20 mmol). Continuing to feed N ₂ For 10 minutes, the system was heated to 80 ℃ until the starting materials were completely reacted. After the completion of the reaction, the product compound B was isolated by column chromatography (1.5 g, yield 30.7%). The product was identified as the target product and had a molecular weight of 744.

Those skilled in the art will recognize that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other compound structures of the present invention. The synthesis method of the compounds with the structures of the formula 7 and the formula 8 can be referred to in the prior literature, such as U.S. Pat. No. 3,124A 1, U.S. Pat. No. 3,25A 1, and Chinese application CN201911046002.3; or methods known to those skilled in the art.

Device embodiment

Inventive device example 1

First, a glass substrate having an 80nm thick Indium Tin Oxide (ITO) anode was cleaned, and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was baked in a glove box to remove moisture. The substrate is then mounted on a substrate support and loaded into a vacuum chamber. The organic layer specified below was at a vacuum level of about 10 ^-8 The deposition was performed sequentially on the ITO anode by thermal vacuum deposition at a rate of 0.2 to 2 a/s in the case of a tray. Co-evaporation of Compound HT with Compound HI-2 (weight ratio 97:3) was used as Hole Injection Layer (HIL), thicknessCompound HT is used as Hole Transport Layer (HTL), thickness +.>Compound EB as electron blockingLayer (EBL), thickness->Then co-evaporating compound BH and compound 4-1 (weight ratio 98:2) to obtain light-emitting layer (EML), with thickness ∈>Using Compound HB as Hole Blocking Layer (HBL), thickness +.>On the hole blocking layer, co-evaporation (weight ratio 40:60) of compound ET and 8-hydroxyquinoline-lithium (Liq) is used as Electron Transport Layer (ETL), thicknessFinally, 8-hydroxyquinoline-lithium (Liq) with a thickness of 1nm was evaporated as an electron injection layer, and 120nm of aluminum was evaporated as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device.

Inventive device example 2

The embodiment of inventive device example 2 was the same as inventive device example 1 except that co-evaporation of compound HT and compound HI-37 (weight ratio 97:3) was used as the Hole Injection Layer (HIL) instead of compound HT and compound HI-2.

Inventive device example 3

The embodiment of inventive device example 3 was the same as that of inventive device example 1, except that compound 8-1 was used in place of compound 4-1 in the light-emitting layer (EML).

Inventive device example 4

The embodiment of inventive device example 4 was the same as inventive device example 2, except that compound 8-1 was used in place of compound 4-1 in the light-emitting layer (EML).

Device example 1

The embodiment of device example 1 was the same as that of inventive device example 1 except that comparative compound a was used in place of compound 4-1 in the light-emitting layer (EML).

Device example 2

The embodiment of device example 2 was the same as device example 1 except that co-evaporation of compound HT and compound HI-37 (weight ratio 97:3) was used as the Hole Injection Layer (HIL) instead of compound HT and compound HI-2.

Device example 3

The embodiment of device example 3 was the same as that of inventive device example 1 except that compound HATCN was used as a Hole Injection Layer (HIL) instead of compound HT and compound HI-2.

Device example 4

The embodiment of device example 4 was the same as device example 3 except that comparative compound a was used in place of compound 4-1 in the light emitting layer (EML).

Device example 5

The embodiment of device example 5 was the same as that of device example 4 except that compound HI-a was used as the Hole Injection Layer (HIL) instead of compound HATCN.

Device example 6

The embodiment of device example 6 was the same as that of inventive device example 3 except that comparative compound B was used in place of compound 8-1 in the light-emitting layer (EML).

Device example 7

The embodiment of device example 7 was the same as device example 6 except that co-evaporation of compound HT and compound HI-37 (weight ratio 97:3) was used as the Hole Injection Layer (HIL) instead of compound HT and compound HI-2.

Device example 8

The embodiment of device example 8 was the same as device example 7 except that compound HI-A was used as a Hole Injection Layer (HIL) instead of compound HT and compound HI-37.

The detailed device layer portion structure and thickness are shown in table 2. Wherein more than one layer of the material used is doped with different compounds in the weight proportions described.

TABLE 2 inventive device examples and partial device structures of the device examples

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The material structure used in the device is as follows:

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calculated by DFT [ GAUSS-09, B3LYP/6-311G (d) ], where the HOMO value of the compound HI-A was-4.77 eV.

The IVL of the device was measured at different current densities and voltages. Wherein Table 3 shows the constant current of 10mA/cm ² Lower test lifetime LT97, power Efficiency (PE), maximum emission wavelength (λ _max ) Half width of peak (FWHM) and CIE data. LT97 represents the time for which the device lifetime decays to 97% of the initial brightness.

TABLE 3 device examples of the invention and device results for the device examples

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Discussion:

at a constant current of 10mA/cm ² The PE of device example 1 was found to be 6.36lm/W, the maximum emission wavelength was found to be 457nm, the CIE was found to be (0.138,0.098), the LT97 was found to be 368 hours, and the half-width was found to be 32.4nm. PE of device example 2 was 6.25lm/W, maximum emission wavelength was 457nm, CIE was (0.139,0.098), LT97 was 315 hours, and half-width was 31.6nm. PE of device example 4 was 6.46lm/W, maximum emission wavelength was 457nm, CIE was (0.138,0.098), LT97 was 269 hours, and half-width was 323nm. In comparison with device example 5 (PE 4.75lm/W, maximum emission wavelength of 458nm, CIE (0.137,0.103), LT97 6 hours, half-width 35.0 nm), device example 1, devicePE of example 2 and device example 4 improved 33.9%, 31.6% and 36.0%, respectively, and life increased 60.3, 51.5 and 43.8 times, respectively. The above results indicate that the power efficiency and the lifetime of the OLED device can be significantly improved by introducing electron-deficient hole injection materials of deep LUMO.

PE of the inventive device example 1 is 6.40lm/W, maximum emission wavelength is 457nm, CIE is (0.138,0.099), LT97 is 606 hours, half-width is 32.4nm; compared with the device example 1, the service life of the device is improved by 64.6 percent. PE of inventive device example 2 was 6.09lm/W, maximum emission wavelength was 458nm, CIE was (0.139,0.098), LT97 was 541 hours, and half-width was 31.7nm; compared with the device example 2, the service life of the device is improved by 71.7 percent. PE of device example 3 was 6.43lm/W, maximum emission wavelength was 457nm, CIE was (0.138,0.099), LT97 was 408 hours, and half-width was 32.4nm; compared with device example 4, the service life of the semiconductor device is improved by 51.7%. The above results show that in the same device structure, using pyrene containing an ortho-deuterated alkyl-substituted aromatic amine structure as a fluorescent light-emitting material can significantly improve the lifetime of an OLED device compared with pyrene containing an ortho-non-deuterated alkyl-substituted aromatic amine structure.

Meanwhile, the life of the invention device example 1 (606 h) and the life of the invention device example 2 (541 h) are respectively improved by 100 and 84.5 times compared with the life of the device example 5 (6 h), and the efficiency of the invention device example 1 (6.4) and the efficiency of the invention device example 2 (6.09) are respectively improved by 34.7% and 28.2% compared with the efficiency of the device example 5 (4.75). The data show that the combination of the pyrene substituted by the ortho-deuterated alkyl aromatic amine structure as the fluorescent luminescent material and the different hole injection materials containing deep LUMO can remarkably improve the service life and efficiency of the OLED device.

The IVL of the device was measured at different current densities and voltages. Wherein Table 4 shows the constant current of 10mA/cm ² Lower test lifetime LT97, power Efficiency (PE), maximum emission wavelength (λ _max ) Half width of peak (FWHM) and CIE data. LT97 represents the time for which the device lifetime decays to 97% of the initial brightness.

TABLE 4 device examples and device results for device examples

PE of device example 6 was 7.30lm/W, maximum emission wavelength was 460 nm, CIE was (0.133,0.127), LT97 was 414 hours, and half-width was 31.4nm. PE of device example 7 was 7.23lm/W, maximum emission wavelength was 460 nm, CIE was (0.133,0.129), LT97 was 329 hours, and half-width was 31.6nm. Compared with device example 8 (PE of 5.32lm/W, maximum emission wavelength of 463nm, CIE of (0.133,0.124), LT97 of 24 hours, half-width of 31.8 nm), PE of device example 6 and device example 7 improved by 37.2% and 35.9%, respectively, and life by 16.3 and 12.7 times, respectively. The above results indicate that the power efficiency and the lifetime of the OLED device can be significantly improved by introducing electron-deficient hole injection materials of deep LUMO.

PE of inventive device example 3 was 7.12lm/W, maximum emission wavelength was 460 nm, CIE was (0.134,0.123), LT97 was 492 hours, half-width was 31.6nm; compared with device example 6, the service life of the semiconductor device is improved by 18.8%. PE of inventive device example 4 was 7.00lm/W, maximum emission wavelength was 460 nm, CIE was (0.134,0.124), LT97 was 451 hours, and half-width was 31.7nm; compared with device example 7, the service life of the semiconductor device is improved by 37.0%. The above results show that in the same device structure, using pyrene containing an ortho-deuterated alkyl-substituted aromatic amine structure as a fluorescent light-emitting material can significantly improve the lifetime of an OLED device compared with pyrene containing an ortho-non-deuterated alkyl-substituted aromatic amine structure.

Meanwhile, the life (492 h) of the inventive device example 3 and the life (451 h) of the inventive device example 4 are respectively improved by 19.5 and 17.8 times as compared with the life (24 h) of the device example 8, and the efficiency (7.12) of the inventive device example 3 and the efficiency (7.00) of the inventive device example 4 are respectively improved by 33.8% and 31.6% as compared with the efficiency (5.32) of the device example 8. The data show that the combination of the pyrene substituted by the ortho-deuterated alkyl aromatic amine structure as the fluorescent luminescent material and the different hole injection materials containing deep LUMO can remarkably improve the service life and efficiency of the OLED device.

As can be seen from the comparison of the above-described sets of device data, when the hole injection materials having different LUMO levels and pyrene having an orthodeuterated alkylarylamine structure substitution or pyrene having an orthodeuterated non-deuterated alkylarylamine structure substitution were used in combination as the fluorescent light-emitting materials, the hole injection layer materials having deeper LUMO levels (HI-37, lumo= -5.57eV, HI-2, lumo= -5.49eV, hatcn, lumo= -4.81 eV) could achieve higher lifetime enhancement (lifetime enhancement of 71.7% for inventive device example 2 and device example 2, lifetime enhancement of 64.6% for inventive device example 1 and device example 4, lifetime enhancement of 51.7% for inventive device example 4 and device example 7, lifetime enhancement of 37.0% for inventive device example 3 and device example 6, and lifetime enhancement of 18.8% for inventive device example 3 and device example 6).

In summary, by using pyrene substituted with ortho-deuterated alkylarylamine structure as fluorescent light-emitting material in combination with different hole injection materials including deep LUMO in the present invention, the lifetime and efficiency of OLED device can be significantly improved. Meanwhile, by using a hole injection material with a deeper LUMO energy level, better hole injection and charge balance are achieved, unexpectedly, a larger effect is exerted on the deuterated material, and the service life of the OLED device can be greatly prolonged when pyrene substituted by an ortho-deuterated alkyl aromatic amine structure is used as a fluorescent light-emitting material.

It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. Thus, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific and preferred embodiments described herein. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. It is to be understood that the various theories as to why the present invention works are not intended to be limiting.

Claims

1. An organic electroluminescent device, comprising:

an anode is provided with a cathode,

a cathode electrode, which is arranged on the surface of the cathode,

wherein the organic layer comprises at least one organic hole injection material; wherein the organic hole injection material has a LUMO less than-4.81 eV;

wherein the organic layer one contains a compound represented by formula 1:

wherein, in the formula 1,

R ₂ to R ₅ ，R ₇ To R ₁₀ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

And, substituent R ₁ And R is ₆ Has a structure represented by formula 3, and R ₁ And R is ₆ Are the same or different:

wherein, in the formula 3,

X ₁ to X ₄ Is selected identically or differently at each occurrence from CR _a1 ，X ₆ To X ₁₀ Is selected identically or differently at each occurrence from CR _a2 ；

L is, identically or differently, selected at each occurrence from a single bond, a substituted or unsubstituted alkylene group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having from 3 to 20 ring carbon atoms, or a substituted or unsubstituted heteroalkylene group having from 1 to 20 carbon atoms;

m is selected identically or differently on each occurrence from 1, 2 or 3;

and m+n=3;

r is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, and combinations thereof;

R _a1 and R is _a2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, and combinations thereof;

Adjacent substituents R _a2 Can optionally be linked to form a ring;

wherein the first organic layer is a light emitting layer, and wherein the compound having formula 1 is an organic light emitting material;

wherein the organic hole injection material is selected from compounds having a structure of formula 7 or having a structure of formula 8:

wherein in formula 8, ring B represents a substituted or unsubstituted carbocyclic ring having 3 to 30 ring atoms;

wherein q is selected from 0,1,2,3 or 4;

wherein in formula 7 and formula 8, X is selected from CR ¹¹ R ¹² ；

Wherein in formula 7, U is selected from CR ¹⁴ The method comprises the steps of carrying out a first treatment on the surface of the Y is selected from N; z is selected identically or differently on each occurrence from O, S or Se;

R ¹¹ ，R ¹² ，R ¹⁴ and is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, cyano, SCN, OCN, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

adjacent substituents R ¹¹ And R is ¹² Can optionally be linked to form a ring.

2. The organic electroluminescent device according to claim 1, wherein the substituent having formula 3 further has a structure represented by formula 4, formula 5 or formula 6:

Wherein in formula 4, formula 5 or formula 6,

x is selected identically or differently at each occurrence from 0, 1, 2 or 3;

X ₆ to X ₁₀ Is selected identically or differently at each occurrence from CR _a2 ；

m is selected identically or differently on each occurrence from 1, 2 or 3;

and m+n=3;

adjacent substituents R _a2 Can optionally be linked to form a ring.

3. The organic electroluminescent device of any of claims 1-2, wherein L is selected, identically or differently, at each occurrence, from a single bond, R is selected, identically or differently, at each occurrence, from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

4. The organic electroluminescent device according to claim 1, wherein the substituent R in formula 1 ₁ And R is ₆ Has a structure represented by formula 3, and R ₁ And R is ₆ Are the same or different; r is R ₂ To R ₅ ，R ₇ To R ₁₀ Is selected identically or differently on each occurrence from the group consisting ofThe group: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, and combinations thereof.

5. The organic electroluminescent device according to claim 1, wherein the substituent R in formula 1 ₁ And R is ₆ Has a structure represented by formula 3, and R ₁ And R is ₆ Are the same or different; r is R ₂ ，R ₄ -R ₅ ，R ₇ And R is ₉ -R ₁₀ Is hydrogen, R ₃ And R is ₈ And is selected identically or differently on each occurrence from hydrogen, substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms.

6. The organic electroluminescent device according to claim 1, wherein X in the formula 3 ₁ To X ₄ Is selected identically or differently at each occurrence from CR _a1 ；X ₆ To X ₁₀ Is selected identically or differently at each occurrence from CR _a2 And adjacent substituents R _a2 Are not connected to form a ring; r is R _a1 And R is _a2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

7. The organic electroluminescent device of any one of claims 1-2, wherein L is, identically or differently, selected at each occurrence from a single bond, a substituted or unsubstituted alkylene group having 1-6 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3-6 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1-6 carbon atoms.

8. The organic electroluminescent device of any one of claims 1-2, wherein the L is, identically or differently, selected from the group consisting of single bond, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene at each occurrence.

9. The organic electroluminescent device of claim 2, wherein Ar is, identically or differently, selected at each occurrence from a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

10. The organic electroluminescent device of claim 2, wherein Ar is selected identically or differently at each occurrence from phenyl or biphenyl.

11. The organic electroluminescent device as claimed in any one of claims 1 to 2, wherein R _a1 And R is _a2 And are selected, identically or differently, at each occurrence from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-10 ring carbon atoms, substituted or unsubstituted aryl groups having 6-12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-12 carbon atoms, and combinations thereof.

12. The organic electroluminescent device as claimed in any one of claims 1 to 2, wherein R _a1 And R is _a2 And is selected, identically or differently, at each occurrence, from: hydrogen, deuterium, fluorine, cyano, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, 4-dimethylcyclohexyl, phenyl, biphenyl.

13. The organic electroluminescent device of any one of claims 1-2, wherein R is, identically or differently, at each occurrence, selected from the group consisting of: hydrogen, deuterium, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, cyclopropyl, deuterated cyclopropyl, n-butyl, deuterated n-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, cyclohexyl, deuterated cyclohexyl, 4-dimethylcyclohexyl, deuterated 4, 4-dimethylcyclohexyl, and combinations thereof.

14. The organic electroluminescent device according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:

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wherein in the above structure, -TMS represents trimethylsilyl.

15. The organic electroluminescent device according to claim 1, wherein LUMO of the organic hole injection material is equal to or less than-4.90 eV.

16. The organic electroluminescent device according to claim 1, wherein LUMO of the organic hole injection material is equal to or less than-5.00 eV.

17. The organic electroluminescent device of claim 1, wherein X is CR ¹¹ R ¹² The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is ¹¹ And R is ¹² And is selected identically or differently on each occurrence from groups having at least one electron withdrawing group.

18. The organic electroluminescent device of claim 1, wherein U is CR ¹⁴ The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is ¹⁴ And is selected identically or differently on each occurrence from groups having at least one electron withdrawing group.

19. The organic electroluminescent device of claim 18, wherein U is CR ¹⁴ The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is ¹⁴ And is selected identically or differently on each occurrence from a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 3 to 30 carbon atoms.

20. The organic electroluminescent device of claim 19, wherein the aryl and heteroaryl groups are substituted with at least one electron withdrawing group.

21. The organic electroluminescent device of any one of claims 17-20, wherein the electron withdrawing group is selected from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Borane, sulfinyl, sulfonyl, phosphinoxy, azaaryl and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Borane-based sulfinyl groupAny of the following groups substituted with one or more of a group, sulfonyl, phosphinoxy, aza-aryl ring groups: alkyl groups having 1-20 carbon atoms, cycloalkyl groups having 3-20 ring carbon atoms, heteroalkyl groups having 1-20 carbon atoms, aralkyl groups having 7-30 carbon atoms, alkoxy groups having 1-20 carbon atoms, aryloxy groups having 6-30 carbon atoms, alkenyl groups having 2-20 carbon atoms, alkynyl groups having 2-20 carbon atoms, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, alkylsilyl groups having 3-20 carbon atoms, arylsilyl groups having 6-20 carbon atoms, and combinations thereof.

22. The organic electroluminescent device of any one of claims 17-20, wherein the electron withdrawing group is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pyrimidinyl, triazinyl, and combinations thereof.

23. The organic electroluminescent device of claim 1, wherein X is selected identically or differently at each occurrence from the group consisting of:

wherein R is ¹ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, cyano, SCN, OCN, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

wherein R is _b ，R _c ，R _d ，R _e And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, cyano, SCN, OCN, substituted or unsubstitutedAlkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof;

And for the saidIn either structure, when R _b ，R _c ，R _d ，R _e At least one of which is a group having an electron withdrawing group;

wherein "×" represents the position of attachment of the X group to formula 7 or formula 8.

24. The organic electroluminescent device of claim 23, wherein R ¹ And is selected identically or differently on each occurrence from the group consisting of: f, CF ₃ Cyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl or triazinyl, and combinations thereof.

25. The organic electroluminescent device of claim 23, for which In either structure, when R _b ，R _c ，R _d ，R _e At least one of which is a group having an electron withdrawing group; the group having an electron withdrawing group is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl or triazinyl, and combinations thereof.

26. The organic electroluminescent device of claim 1, wherein X is selected identically or differently at each occurrence from the group consisting of:

wherein "×" represents the position at which the X group is attached in formula 7 or formula 8.

27. The organic electroluminescent device of claim 26, wherein X is selected identically or differently at each occurrence from A1 or A2.

28. The organic electroluminescent device of claim 23, wherein R ¹¹ ，R ¹² ，R ¹⁴ And R is ¹ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, methyl, isopropyl, C ₂ F ₅ Phenyl, methoxyphenyl, p-methylphenyl, 2, 6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, F, CF ₃ CN, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, pyridyl, vinyl substituted with one or more of CN and CF3, vinyl substituted with F, CN and CF ₃ Phenyl or biphenyl groups, and combinations thereof.

29. The organic electroluminescent device of claim 1, wherein the compound having the structure of formula 7 and the structure of formula 8 is selected from the group consisting of:

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30. the organic electroluminescent device of claim 1, wherein the light emitting layer further comprises a host material.

31. The organic electroluminescent device of claim 30, the host material comprising a compound having formula 9:

Wherein R is _d1 To R _d8 Each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, phosphino, sulfinyl, sulfonyl, and combinations thereof;

R _d9 and R is _d10 Each independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstitutedHeteroaryl groups having 3 to 30 carbon atoms.

32. The organic electroluminescent device according to claim 1, wherein the second organic layer is a hole injection layer formed solely from the hole injection material.

33. The organic electroluminescent device according to claim 1, wherein the second organic layer is a hole injection layer or a hole transport layer.

34. The organic electroluminescent device of claim 33, wherein the second organic layer is a hole injection layer or a hole transport layer; the hole injection layer or hole transport layer further comprises at least one hole transport material comprising a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylenevinylene compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the molar doping ratio of the hole injection material to the hole transport material is 10000:1 to 1:10000.

35. an electronic device comprising the organic electroluminescent device of any one of claims 1-34.