CN116056485A

CN116056485A - Organic electroluminescent device

Info

Publication number: CN116056485A
Application number: CN202111261611.8A
Authority: CN
Inventors: 丁尚; 王静; 庞惠卿; 高亮; 崔至皓; 李锋
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2021-10-28
Filing date: 2021-10-28
Publication date: 2023-05-02

Abstract

An organic electroluminescent device is disclosed. The organic electroluminescent device includes an anode, a cathode, a light emitting layer disposed between the anode and the cathode, and a first organic layer disposed between the anode and the light emitting layer, the first organic layer including a first compound having a structure of formula 1 and a second compound having a structure of formula 2. The organic electroluminescent device disclosed by the invention has the excellent characteristics of high efficiency and long service life, and can provide better device performance. Also disclosed are an electronic assembly comprising the organic electroluminescent device and a compound combination comprising a first compound having the structure of formula 1 and a second compound having the structure of formula 2.

Description

Organic electroluminescent device

Technical Field

The present invention relates to an organic electronic device, and in particular, to an organic electroluminescent device. And more particularly, to an organic electroluminescent device including a first compound having a structure of formula 1 and a second compound having a structure of formula 2 in a first organic layer, and an electronic component including the same.

Background

The organic electroluminescent device converts electric energy into light by applying a voltage across the device. In general, an organic electroluminescent device includes an anode, a cathode, and an organic layer between the anode and the cathode. The organic layers of the electroluminescent device include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (including host materials and doped materials), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. The materials constituting the organic layer may be classified into a hole injecting material, a hole transporting material, an electron blocking material, a host material, a light emitting material, an electron buffer material, a hole blocking material, an electron transporting material, an electron injecting material, and the like according to the functions of the materials. When a bias is applied to the device, holes are injected from the anode to the light emitting layer and electrons are injected from the cathode to the light emitting layer. The holes and electrons meet at the light-emitting layer to form excitons, which recombine to emit light. The hole injection layer is one of important functional layers affecting the performance of the organic electroluminescent device, and the selection and collocation of materials seriously affect the performance of the device. Since organic electroluminescent devices having characteristics such as high efficiency and long service life are commercially desired, the development of a novel hole injection layer is a very critical research field.

In the early OLED device, a layer of organic material is arranged between an anode and a light-emitting layer, and the functions of hole injection, hole transmission and even electron blocking are considered, the structure of the device is limited by a single hole transmission material, and a large hole injection barrier exists between the anode and the organic layer, so that the energy level cannot be matched more ideally, and the ideal performance is difficult to obtain; with the increasing demands of the industry for device performance, the demands for performance of a hole transport region between an anode and a light emitting layer are also increasing, and then the hole transport material is further subdivided into a hole injection layer and a hole transport layer, and a single triarylamine material is generally used as the hole injection layer, wherein the common triarylamine material is as follows:

in the most advanced device structure in the current industry, a plurality of organic layers are generally disposed between an anode and a light emitting layer to respectively realize a hole injection function, a hole transport function and an electron blocking function. To obtain a better hole injection effect, a proportion of p-type conductive doping material is often doped in a hole transport material (for example, arylamine compounds) in the hole injection layer, and common p-type conductive doping materials include:

In the structure of the device in commercial use at present, the HOMO energy level of the hole transport material is usually about-5.10 eV, but the HOMO energy level of the host material in the common luminescent layer is usually about-5.40 eV or below, and is far deeper than that of the common hole transport material, so that an energy level difference of about 0.30eV is formed between the hole transport material and the host material, namely, a higher potential barrier is encountered when holes enter the luminescent layer from the transport layer, and the hole transport is affected.

In order to solve the problem, a method is generally adopted in the industry to add a layer of electron blocking layer material with HOMO energy level between the hole transport layer and the light emitting layer, namely, a multi-layer structure is established between the hole injection layer and the light emitting layer, so that a potential energy progressive structure is formed, the high efficiency of hole transport between layers in the device is realized, and the purpose of optimizing the device performance is achieved. Another widely accepted solution by researchers in the industry is to use hole transporting materials with deeper HOMO levels to reduce the energy level difference between the hole transporting material and the host material, which has not been widely adopted because of the lack of a p-type conductivity dopant material used as a hole injection layer in combination with deep HOMO level hole transporting materials and to maintain excellent device performance. In order to obtain good hole injection characteristics, the LUMO level of the p-type conductive doped material needs to be equal to or deeper than the HOMO level of the hole transporting material, but the LUMO level of the p-type conductive doped material currently in commercial use is generally shallow, and as described above, the HOMO level of the commercial hole transporting material used as the hole injection layer is generally about-5.10 eV. The development of p-type conductive doping materials with deeper LUMO energy levels breaks the current situation and provides more possibilities for hole injection and transport material selection.

Applicant's prior U.S. patent application No. US20200062778A1 discloses a composition having dehydrobenzobisoxazole, dehydrobenzodithiazole or dehydrobenzodiselenzole and the like

The organic compound of the compound has deeper LUMO energy level, so the hole transport material which can be matched with the compound can be selected to be a material with deeper energy level. In the above patent application, only the application of such compounds as p-type conductive doping materials to organic electroluminescent devices is disclosed, but the patent does not disclose or teach the effect of such p-type conductive doping materials on the device performance when used as a hole injection layer in combination with materials having a bicarbazole skeleton structure.

Compounds having a dicarbazole skeleton are generally used as host materials for the light-emitting layer, as disclosed in US2020377489A1 and US20210130304 A1; or electron blocking materials, as disclosed in CN111675707A and CN111100129A, but do not disclose compounds having a dicarbazole skeleton and compounds having a dicarbazole skeleton

When the p-type conductive doping material of the structure is matched with the p-type conductive doping material to be used as a hole injection material, the p-type conductive doping material has influence on the performance of the device.

With the continuous accumulation and optimization of OLED materials and devices, the demands of the industry for device performance are further increased, and how to enable OLED end products to reduce voltage and obtain higher device efficiency, such as current efficiency, power efficiency and external quantum efficiency, is an urgent problem for researchers in the industry. Different p-type conductive doping materials and different hole transport materials can generate different hole injection effects, the matching degree of the p-type conductive doping materials and the hole transport materials is particularly important, and the interface injection effect is better as the matching degree is higher. In order to obtain better hole injection effect and enable the performance of the device to reach a higher level, on one hand, research and development of more excellent p-type conductive doping materials and/or more excellent hole transport materials are very important; on the other hand, screening a combination of a suitable hole transporting material and a p-type conductive doping material is also an important way to develop a novel hole injection layer.

Disclosure of Invention

The present invention aims to provide a series of novel organic electroluminescent devices to solve at least part of the above problems. The novel organic electroluminescent device comprises an anode, a cathode, a light emitting layer arranged between the anode and the cathode, and a first organic layer arranged between the anode and the light emitting layer, wherein the first organic layer at least comprises a first compound with a structure of formula 1 and a second compound with a structure of formula 2. The novel material combination composed of the first compound and the second compound can be used in an organic electroluminescent device, so that the organic electroluminescent device has excellent characteristics of high efficiency and long service life, and better device performance can be provided.

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

an anode is provided with a cathode,

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

a light-emitting layer disposed between the anode and the cathode, and a first organic layer disposed between the anode and the light-emitting layer, wherein the first organic layer comprises at least a first compound and a second compound;

wherein the first compound has a structure represented by formula 1:

in the formula (1) of the present invention,

ZX ₁ and and YZ₂ Each occurrence is identically or differently selected from NOR, ', SC or RS ' e '; r' ", O, S or Se;

R, R 'and R' eachThe second occurrence is identically or differently selected 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;

at least one of R, R 'and R' is a group having at least one electron withdrawing group;

Adjacent substituents R, R ', R ", and R'" in formula 1 can optionally be linked to form a ring;

the second compound has a structure represented by formula 2:

wherein ,

L _x each occurrence is identically or differently selected 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 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;

Ar ₁ and Ar₂ And is selected identically or differently on each occurrence from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 3 to 3Heteroaryl groups of 0 carbon atoms and combinations thereof;

X ₁ -X ₁₆ is selected identically or differently on each occurrence from C, CR _x Or N; wherein X is ₅ -X ₈ At least one of which is selected from C and is combined with L _x Are connected; x is X ₉ -X ₁₂ At least one of which is selected from C and is combined with L _x Are connected;

R _x 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 heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl 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 alkynyl 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 alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituent R in formula 2 _x Can optionally be linked into a ring.

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

According to another embodiment of the present invention, there is also disclosed a combination of compounds comprising a first compound and a second compound, the first compound and the second compound being as shown in any of the previous embodiments.

The novel organic electroluminescent device comprises an anode, a cathode, a light emitting layer arranged between the anode and the cathode, and a first organic layer arranged between the anode and the light emitting layer, wherein the first organic layer comprises a first compound with a structure of formula 1 and a second compound with a structure of formula 2. The charge injection and transmission effects of the device are improved through the effective matching of two materials with specific structures in the first organic layer; the novel organic electroluminescent device has excellent characteristics of high efficiency and long service life, and can provide better device performance.

Drawings

Fig. 1 is a schematic view of an organic light emitting device that may contain the organic electroluminescent devices disclosed herein.

Fig. 2 is a schematic view of another organic light emitting device that may contain the organic electroluminescent devices 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. U.S. patent to Thompson et al, incorporated by reference in its entirety Examples of host materials are disclosed in U.S. Pat. No. 6,303,238. 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. Examples of cathodes are disclosed in U.S. Pat. nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, including composite cathodes having a thin layer of metal, such as Mg: ag, with an overlying transparent, electrically 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-as used herein, includes straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. 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. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. In addition, the alkyl group may be optionally substituted.

Cycloalkyl-as used herein, includes cyclic alkyl. Cycloalkyl groups may be cycloalkyl groups having 3 to 20 ring carbon atoms, preferably 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl are preferred. In addition, cycloalkyl groups may be optionally substituted.

Heteroalkyl-as used herein, a heteroalkyl comprises an alkyl chain in which one or more carbons is replaced by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron. The heteroalkyl group may be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, t-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl. In addition, heteroalkyl groups may be optionally substituted.

Alkenyl-as used herein, covers straight chain, branched chain, and cyclic alkylene groups. Alkenyl groups may be alkenyl groups containing 2 to 20 carbon atoms, preferably alkenyl groups having 2 to 10 carbon atoms. Examples of alkenyl groups include ethenyl, propenyl, 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, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. In addition, alkenyl groups may be optionally substituted.

Alkynyl-as used herein, straight chain alkynyl is contemplated. The alkynyl group may be an alkynyl group containing 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl and the like. Among the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl and phenylethynyl. In addition, alkynyl groups may be optionally substituted.

Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. The aryl group may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 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. 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-terphenylBenzene-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methylbiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-tetrabiphenyl. In addition, aryl groups may be optionally substituted.

Heterocyclyl or heterocycle-as used herein, non-aromatic cyclic groups are contemplated. The non-aromatic heterocyclic group includes a saturated heterocyclic group having 3 to 20 ring atoms and an unsaturated non-aromatic heterocyclic group having 3 to 20 ring atoms, at least one of which is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms including at least one hetero atom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxacycloheptatrienyl, thietaneyl, azepanyl and tetrahydrosilol. In addition, the heterocyclic group may be optionally substituted.

Heteroaryl-as used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms, at least one of which is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms. Heteroaryl also refers to heteroaryl. The heteroaryl group may be a heteroaryl group having 3 to 30 carbon atoms, preferably a heteroaryl group having 3 to 20 carbon atoms, more preferably a heteroaryl group having 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-as used herein, is represented by-O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or-O-heterocyclyl. Examples and preferred examples of the alkyl group, cycloalkyl group, heteroalkyl group and heterocyclic group are the same as described above. The alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, the alkoxy group may be optionally substituted.

Aryloxy-as used herein, is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. The aryloxy group may be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenoxy. In addition, the aryloxy group may be optionally substituted.

Aralkyl-as used herein, encompasses aryl-substituted alkyl. The aralkyl group may be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 13 carbon atoms. 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. In addition, aralkyl groups may be optionally substituted.

Alkyl-as used herein, alkyl-substituted silicon groups are contemplated. The silyl group may be a silyl group having 3 to 20 carbon atoms, preferably a silyl group having 3 to 10 carbon atoms. Examples of the alkyl silicon group include trimethyl silicon group, triethyl silicon group, methyldiethyl silicon group, ethyldimethyl silicon group, tripropyl silicon group, tributyl silicon group, triisopropyl silicon group, methyldiisopropyl silicon group, dimethylisopropyl silicon group, tri-t-butyl silicon group, triisobutyl silicon group, dimethyl-t-butyl silicon group, and methyldi-t-butyl silicon group. In addition, the alkyl silicon group may be optionally substituted.

Arylsilane-as used herein, encompasses at least one aryl-substituted silicon group. The arylsilane group may be an arylsilane group having 6 to 30 carbon atoms, preferably an arylsilane group having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenyl silyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl. In addition, arylsilane groups may be optionally substituted.

Alkyl germanium group-as used herein, alkyl substituted germanium groups are contemplated. The alkylgermanium group may be an alkylgermanium group having 3 to 20 carbon atoms, preferably an alkylgermanium group having 3 to 10 carbon atoms. Examples of alkyl germanium groups include trimethyl germanium group, triethyl germanium group, methyl diethyl germanium group, ethyl dimethyl germanium group, tripropyl germanium group, tributyl germanium group, triisopropyl germanium group, methyl diisopropyl germanium group, dimethyl isopropyl germanium group, tri-t-butyl germanium group, triisobutyl germanium group, dimethyl-t-butyl germanium group, methyl-di-t-butyl germanium group. In addition, alkyl germanium groups may be optionally substituted.

Arylgermanium group-as used herein, encompasses at least one aryl or heteroaryl substituted germanium group. The arylgermanium group may be an arylgermanium group having 6-30 carbon atoms, preferably an arylgermanium group having 8 to 20 carbon atoms. Examples of aryl germanium groups include triphenylgermanium group, phenylbiphenyl germanium group, diphenylbiphenyl germanium group, phenyldiethyl germanium group, diphenylethyl germanium group, phenyldimethyl germanium group, diphenylmethyl germanium group, phenyldiisopropylgermanium group, diphenylisopropylgermanium group, diphenylbutylgermanium group, diphenylisobutylglycol group, and diphenyltert-butylgermanium group. In addition, the arylgermanium group may be optionally substituted.

The term "aza" in azadibenzofurans, azadibenzothiophenes and the like means that one or more C-H groups in the corresponding aromatic fragment are replaced by a nitrogen atom. 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 heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermanium, substituted arylgermanium, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups, which may be substituted with one or more groups selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted cycloalkyl having 1 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, unsubstituted arylgermanium groups having 6 to 20 carbon atoms, unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphine groups, 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, polysubstituted means inclusive of disubstituted 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.

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 can be monocyclic or polycyclic (including spiro, bridged, fused, etc.), 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:

the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that the two substituents bound to further distant carbon atoms 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 optionally be linked to form a ring is also intended to be taken to mean that, in the case where one of the adjacent two substituents 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,

a light-emitting layer disposed between the anode and the cathode, and a first organic layer disposed between the anode and the light-emitting layer, wherein the first organic layer comprises at least a first compound and a second compound; wherein the first compound has a structure represented by formula 1:

in the formula (1) of the present invention,

x and Y are, identically or differently, selected from NR ', CR ' R ', O, S or Se;

Z ₁ and Z₂ Is selected identically or differently on each occurrence from O, S or Se;

r, R 'and R' are 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;

the second compound has a structure represented by formula 2:

wherein ,

Ar ₁ and Ar₂ 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, and combinations thereof;

Adjacent substituent R in formula 2 _x Can optionally be linked into a ring.

In this embodiment, adjacent substituents R, R ', R "and R'" in formula 1 can optionally be linked to form a ring, and it is intended that in formula 1, adjacent substituent groups, such as adjacent substituents R "and R '", adjacent substituents R and R' ", and two adjacent substituents R, any one or more of these adjacent substituent groups can be linked to form a ring. Obviously, none of these adjacent groups of substituents may be linked to form a ring.

Herein, adjacent substituents R in formula 2 _x Can optionally be linked to form a ring, is intended to mean that in formula 2, two adjacent substituents R _x Any one or more of the group consisting of can be linked to form a ring. Obviously, these adjacent substituents R _x Or none may be joined to form a ring.

According to one embodiment of the invention, wherein X and Y are, identically or differently, selected from NR 'or CR' R ', wherein R', R 'and R' are groups having at least one electron withdrawing group.

According to one embodiment of the invention, wherein X and Y are, identically or differently, selected from NR ' or CR ' R ', R, R ' and R ' are groups having at least one electron withdrawing group.

According to one embodiment of the invention, wherein X and Y are selected identically or differently on each occurrence from O, S or Se, at least one of R being a group having at least one electron withdrawing group.

According to one embodiment of the invention, wherein X and Y are, identically or differently, selected for each occurrence from O, S or Se, each R being a group having at least one electron withdrawing group.

According to one embodiment of the invention, wherein the Hammett constant of the electron withdrawing group is not less than 0.05, preferably not less than 0.3, more preferably not less than 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, phosphinyloxy, azaaromatic ring groups, and groups selected from the group consisting of 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, phosphinyloxy, 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 and Y are, identically or differently, selected from the group consisting of:

wherein ,R₂ 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;

preferably, R ₂ 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, triazinyl, and combinations thereof;

wherein V and W are, identically or differently, selected from CR for each occurrence _v R _w ，NR _v O, S or Se;

wherein Ar is the same or different at each occurrence and is selected 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_a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v and R_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 Borane, sulfinyl, sulfonyl, phosphinoxy, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstitutedUnsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms, substituted or unsubstituted alkoxy having 1-20 carbon atoms, substituted or unsubstituted aryloxy having 6-30 carbon atoms, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted alkynyl having 2-20 carbon atoms, substituted or unsubstituted aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms, substituted or unsubstituted alkylsilyl having 3-20 carbon atoms, substituted or unsubstituted arylsilyl having 6-20 carbon atoms, and combinations thereof;

Wherein A is a group having at least one electron withdrawing group, and for any of the structures, when R _a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v and R_w When one or more of them occur, R _a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v and R_w Is a group having at least one electron withdrawing group; preferably, the group having at least one 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, triazinyl, and combinations thereof.

In this embodiment, "" means the position where the X and Y groups are attached to the dehydrobenzobisoxazole ring, dehydrobenzodithiazole ring or dehydrobenzodiselenole ring in formula 1.

According to one embodiment of the invention, wherein X and Y are

Wherein "×" represents the position where the X and Y groups are attached to the dehydrobenzobisoxazole ring, the dehydrobenzodithiazole ring or the dehydrobenzodiselenole ring in formula 1.

According to one embodiment of the invention, wherein R 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 Boranyl, sulfinyl, sulfonyl, phosphinoxy, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted alkoxy having 1 to 20 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, and is substituted by halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Any one of the following groups substituted with one or more of borane, sulfinyl, sulfonyl, and phosphinyloxy: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

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, 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, substituted by CN or CF ₃ Is substituted by one or more vinyl groups, by CN or CF ₃ One of the substituted ethynyl, dimethylphosphinyloxy, diphenylphosphinyloxy, F, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, substituted with F, CN or CF ₃ Phenyl or biphenyl groups, tetrafluoropyridyl, pyrimidinyl, triazinyl, diphenylborane groups, oxaborolidinyl groups, and combinations thereof.

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

/>

in the present embodiment of the present invention, in the present embodiment,

represents the position where the R group is attached to the dehydrobenzodioxazole ring, the dehydrobenzodithiazole ring or the dehydrobenzodiselenzole ring in formula 1.

According to one embodiment of the present invention, wherein two R are the same in one first compound represented by formula 1.

According to one embodiment of the invention, wherein the first compound is selected from the group consisting of compound 1 to compound 182; the specific structure of compounds 1 to 182 is seen in claim 6.

According to one embodiment of the present invention, wherein the second compound has a structure represented by formula 2-a:

wherein ,

Ar ₁ and Ar₂ The same or different at each occurrence is selected from substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, or combinations thereof;

X ₁ -X ₅ 、X ₇ -X ₁₀ and X₁₂ -X ₁₆ Is selected from CR, identically or differently at each occurrence _x Or N;

R _x 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 heterocyclyl having 3 to 20 ring 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 alkynyl 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 alkylgermanium having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl Sulfonyl, phosphino, and combinations thereof;

adjacent substituents R in formula 2-a _x Can optionally be linked into a ring.

In this embodiment, "adjacent substituents R in formula 2-a _x Being able to be optionally linked to form a ring "is intended to mean that in formula 2-a, two adjacent substituents R _x Any one or more of the group consisting of can be linked to form a ring. Obviously, these adjacent substituents R _x Or none may be joined to form a ring.

According to one embodiment of the invention, wherein Ar ₁ and Ar₂ The same or different at each occurrence is selected from substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 20 carbon atoms, or combinations thereof.

According to one embodiment of the invention, wherein Ar ₁ and Ar₂ The groups are selected, identically or differently, for each occurrence, from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted quinolinyl, or combinations thereof.

According to an embodiment of the present invention, wherein the second compound has a structure represented by formula 2-b:

wherein ,

L _x each occurrence is identically or differently selected 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 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a group thereofCombining;

Ar ₂ the same or different at each occurrence is selected from substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, or combinations thereof;

V ₁ -V ₉ is selected identically or differently on each occurrence from C, CR _v ' or N;

R _x and R_v ' 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 heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl 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 alkynyl 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 alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R in formula 2-b _x and R_v ' can optionally be linked into a ring.

In this embodiment, "adjacent substituents R in formula 2-b _x and R_v 'can optionally be linked to form a ring', is intended to mean that in formula 2-b,two adjacent substituents R _x Two adjacent substituents R _v ' can be linked to form a ring. Obviously, these adjacent substituents R _x and R_v Neither may be joined to form a ring.

According to one embodiment of the present invention, wherein Ar in formula 2-b ₂ The same or different at each occurrence is selected from substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 20 carbon atoms, or combinations thereof.

According to one embodiment of the present invention, wherein Ar in formula 2-b ₂ The groups are selected, identically or differently, for each occurrence, from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted quinolinyl, or combinations thereof.

According to one embodiment of the invention, wherein L _x The groups are selected, identically or differently, on each occurrence from single bonds, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene groups having 3 to 20 carbon atoms, or combinations thereof.

According to one embodiment of the invention, wherein L _x The groups are selected, identically or differently, on each occurrence, from single bonds, substituted or unsubstituted phenylene groups, substituted or unsubstituted biphenylene groups, or combinations thereof.

According to one embodiment of the invention, wherein L _x Each occurrence is a single bond.

According to one embodiment of the present invention, wherein the second compound has a structure represented by formula 2-c:

wherein ,

V ₁ -V ₁₈ is selected identically or differently on each occurrence from C, CR _v ' or N;

Adjacent substituents R in formula 2-c _x and R_v ' can optionally be linked into a ring.

In this embodiment, "adjacent substituents R in formulas 2-c _x and R_v 'being able to be optionally linked to form a ring', it is intended to mean that in formula 2-c two adjacent substituents R _x Two adjacent substituents R _v ' can be linked to form a ring. Obviously, these adjacent substituents R _x and R_v Neither may be joined to form a ring.

According to one embodiment of the invention, wherein X ₁ -X ₁₆ Is selected identically or differently on each occurrence from C or CR _x 。

According to one embodiment of the invention, wherein X ₁ -X ₅ 、X ₇ -X ₁₀ and X₁₂ -X ₁₆ Is selected from CR, identically or differently at each occurrence _x 。

According to one embodiment of the invention, wherein X ₁ -X ₁₆ Is selected identically or differently on each occurrence from C, CR _x Or N, and at least one of them is selected from N, e.g. X ₁ -X ₁₆ One or two of which are selected from N.

According to one embodiment of the invention, wherein X ₁ -X ₅ 、X ₇ -X ₁₀ and X₁₂ -X ₁₆ Is selected from CR, identically or differently at each occurrence _x Or N, and at least one of them is selected from N, e.g. X ₁ -X ₅ 、X ₇ -X ₁₀ and X₁₂ -X ₁₆ One or two of which are selected from N.

According to one embodiment of the invention, wherein R _x and R_v ' 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, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, and combinations thereof.

According to one embodiment of the invention, wherein R _x and R_v ' is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R _x and R_v ' identical or at each occurrenceDifferently selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and combinations thereof.

According to one embodiment of the invention, wherein the second compound is selected from the group consisting of compound X-1 to compound X-171; the specific structure of said compounds X-1 to X-171 is seen in claim 13.

According to one embodiment of the invention, the mass ratio of the first compound to the second compound in the first organic layer ranges from 1:10000 to 10000:1.

According to one embodiment of the invention, the mass ratio of the first compound to the second compound in the first organic layer ranges from 1:1000 to 100:1.

According to one embodiment of the invention, the mass ratio of the first compound to the second compound in the first organic layer ranges from 1:100 to 10:1.

According to one embodiment of the invention, the mass ratio of the first compound to the second compound in the first organic layer ranges from 1:100 to 1:1.

According to one embodiment of the invention, the organic electroluminescent device further comprises a second organic layer disposed between the anode and the light emitting layer, the second organic layer comprising a second compound.

According to one embodiment of the invention, wherein the organic electroluminescent device further comprises a third organic layer arranged between the anode and the light emitting layer, wherein the third organic layer comprises a different compound than the second organic layer.

According to one embodiment of the invention, the first organic layer is in direct contact with the anode.

According to another embodiment of the present invention, an electronic component is also disclosed, which includes an organic electroluminescent device, and the specific structure of the organic electroluminescent device is as shown in any one of the foregoing embodiments.

According to one embodiment of the invention, the electronic component is a display component or a lighting component.

Combined with other materials

The materials described herein for specific layers in an organic light emitting 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 light emitting device may be used in combination with a variety of other materials present in the device. For example, the combination of compounds disclosed herein can be used in combination with a variety of light-emitting dopants, 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 device of the present invention, charge injection, transport layers, such as hole injection layers, hole transport layers, electron transport layers, and electron injection layers, may be included; may also comprise a light-emitting layer comprising at least one light-emitting dopant, which may be a fluorescent light-emitting dopant and/or a phosphorescent light-emitting dopant, and at least one host compound; an electron blocking layer, a hole blocking layer may also be included.

In the present invention, the values of HOMO levels (highest occupied orbitals) and LUMO levels (lowest unoorbitals) of all compounds were measured by Cyclic Voltammetry (CV). The test uses an electrochemical workstation model CorrTest CS120, manufactured by marc instruments inc, and uses a three electrode working system: platinum disk electrode as working electrode, ag/AgNO ₃ The electrode is a reference electrode, and the platinum wire electrode is an auxiliary electrode. The test temperature was 25℃and the test compound was formulated as 10 using anhydrous DCM as solvent and tetrabutylammonium hexafluorophosphate at 0.1mol/L as supporting electrolyte ^-3 And (3) introducing nitrogen into the solution in mol/L for 10min to deoxidize before testing. Instrument parameter setting: the scan rate was 100mV/s, the potential spacing was 0.5mV, and the test window was 1V to-0.5V. Herein, all "HOMO energy levels" and "LUMO energy levels" are negative, and the smaller the value (i.e., the larger the absolute value), the deeper the energy level.

Table 1 lists HOMO or LUMO energy levels of some compounds, where "/" indicates that no relevant values were tested. It can be seen that the LUMO level of the compound 70 of the present invention as a p-type conductivity dopant material is deeper than that of commercial material PD. Meanwhile, the HOMO energy level of the compound X-127 as a hole transport material was also deeper than HT, reaching-5.36 ev. Thus, compound 70 is a p-type conductivity dopant material that is more suitable for use with compound X-127.

TABLE 1 energy level data for some of the compounds

The structure of the above-tested materials is as follows:

device embodiment

The first compound and the second compound used in the present invention can be obtained by referring to the preparation methods in the prior art, and are not described herein. The method of manufacturing the electroluminescent device is not limited, and the following examples are only examples and should not be construed as limiting. Those skilled in the art will be able to make reasonable modifications to the preparation methods of the following examples in light of the prior art. The proportion of the various materials in the luminescent layer is not particularly limited, and a person skilled in the art can reasonably select the materials within a certain range according to the prior art, for example, the main material can account for 70% -99% and the luminescent material can account for 1% -30% based on the total weight of the luminescent layer materials; or the main material can account for 90% -98%, the luminescent material can account for 2% -10%, or the main material can account for 87% -98%, and the luminescent material can account for 2% -13%. In addition, the main body material can be one or two materials, wherein the proportion of the two main body materials to the main body material can be 99:1 to 1:99; alternatively, the ratio may be 80:20 to 20:80; alternatively, the ratio may be 60:40 to 40:60. 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.

Example 1: a fluorescent blue organic electroluminescent device 100 was prepared as shown in fig. 1.

First, a glass substrate having a thickness of 0.7mm and having a pre-patterned thereon was used

A thick Indium Tin Oxide (ITO) was used as the anode 110, and after washing the substrate with deionized water and a detergent, the ITO surface was treated with oxygen plasma and UV ozone. Subsequently, the substrate is baked in a glove box to remove moisture, andloading the support into a vacuum chamber. The organic layer specified below was at a vacuum level of about 10 ^-6 In case of Torr +.>

Sequentially evaporating on the anode layer by vacuum thermal evaporation: first, compound X-127 and compound 70 were simultaneously evaporated as a hole injection layer (HIL, 97:3,

) 120, vapor deposition compound X-127 was used as hole transport layer (HTL,/->

) 130, evaporation compound EB is used as electron blocking layer (EBL, ">

) 140, on which a compound BH and a compound BD are simultaneously evaporated as light-emitting layers (EML, 96:4, ->

) 150, evaporation of the compound HB as hole blocking layer (HBL, -/->

) 160, the compounds ET and Liq were co-deposited as electron transport layers (ETL, 40:60,/for>

) 170, vapor plating->

Liq of thickness acts as an Electron Injection Layer (EIL) 180. Finally, metallic aluminum was evaporated as Cathode (Cathiode, >

) 190. The device was then transferred back to the glove box and packaged with a glass cover slip to complete the device.

Comparative example 1:the same procedure as in example 1 was followed, except that compound X-127 and compound PD were simultaneously vapor-deposited as a hole injection layer (HIL, 97:3,

)。

comparative example 2: the same procedure as in example 1 was followed, except that compound HT and compound 70 were simultaneously evaporated as a hole injection layer (HIL, 97:3,

) Vapor deposition compound HT is used as hole transport layer (HTL,/or the like)>

)。

Comparative example 3: the same procedure as in example 1 was followed, except that compound HT and compound PD were simultaneously evaporated as hole injection layers (HIL, 97:3,

)。

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

Table 2 partial device structures of example 1 and comparative examples 1 to 3

The structure of the materials used in the device is as follows:

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table 3 shows the device performance of example 1 and comparative examples 1 to 3. Wherein, the color coordinates, the voltage V, the current efficiency CE, the power efficiency PE and the external quantum efficiency EQE are all 15mA/cm in current density ² The device lifetime LT95 data is measured at 80mA/cm ² Data for the decay of device brightness to 95% of the initial brightness under drive.

Table 3 device performance for example 1 and comparative examples 1-3

Table 3 shows the results of partial performance tests of electroluminescent devices comprising different combinations of p-type conductivity doping materials and hole transporting materials, and it can be seen from the color coordinates that the examples shown are substantially identical to the color coordinates of the comparative examples.

In example 1, a device structure of the specific structure disclosed in the present invention was used in which the hole transporting material compound X-127 and the p-type conductive dopant compound 70 were combined. In comparative example 1, a device structure in which a specific structure of a transport material compound X-127 was combined with a conventional p-type conductive dopant material compound PD was used. The voltage of example 1 was reduced by 0.68V, 13% compared to comparative example 1; the power efficiency is improved by 0.7lm/W, and is improved by 13%; the service life LT95 is prolonged from 4h to 317h, which is improved by 78.3 times, and the current efficiency is equivalent. It should be noted that, in both example 1 and comparative example 1, the same second compound X-127 was used, but the voltages of the two compounds were greatly different, and the main reason is that the HOMO level of the compound X-127 was deeper, which was-5.36 eV, and in comparative example 1, when used in combination with the p-type conductive doping material PD of shallow LUMO, the voltage was higher because the energy levels of the two compounds were greatly different (0.32 eV), the energy levels were not matched, the p-type doping effect was not obvious, and the hole injection was poor; but when the compound 70 is matched, the energy level difference of the compound and the compound is 0.19eV, the energy levels are more matched, the p-type doping effect is obvious, the hole injection is good, and the voltage is greatly reduced; meanwhile, the voltage is reduced, so that the device achieves better carrier balance, and therefore, the efficiency and the service life of the device are improved, and particularly, the service life of the device is greatly improved. From the above, the combination of the first compound 70 and the second compound X-127 can reduce the voltage of the device, and obviously improve the efficiency and the service life.

In comparative example 2, a device structure in which a conventional transport material HT was combined with a p-type conductive dopant material compound 70 of a specific structure was used. Compared with comparative example 2, the current efficiency of the device is improved by 1.6cd/A and is improved by 23%; the power efficiency is improved by 1.0lm/W, and the power efficiency is improved by 20%; the external quantum efficiency is improved by 1.66%, and the external quantum efficiency is improved by 22%; the service life LT95 is improved from 140h to 317h by 1.26 times. Notably, the voltages of comparative example 2 and example 1 are substantially equivalent, mainly because the compound HT is more energy-matched to the p-type conductivity dopant compound 70 of the deep LUMO (the difference between the two energy levels is 0.08 eV); but the performance such as efficiency and lifetime is still inferior to the combination of the second compound X-127 and the first compound 70. Thus, it was further demonstrated that the use of the first compound 70 in combination with the second compound X-127 may result in better device performance.

In comparative example 3, a device structure in which a conventional transfer material HT was combined with a conventional p-type conductive doping material PD was used. The voltage of example 1 was reduced by 0.30V, 6% compared to comparative example 3; the current efficiency is improved by 1.7cd/A, and the current efficiency is improved by 24%; the power efficiency is improved by 1.5lm/W, and is improved by 33%; the external quantum efficiency is improved by 1.76%, and the external quantum efficiency is improved by 23%; the service life is prolonged from 5h to 317h, and is improved by 62.4 times. Thus, it was once again demonstrated that the combined use of the first compound 70 of the present invention with the second compound X-127 can obtain more excellent device performance.

In summary, the first compound 70 and the second compound X-127 used in the embodiment of the present invention are combined and matched, so that the collocation between materials is better, the hole injection capability is higher, and the performance of the prepared organic electroluminescent device is more excellent.

The organic electroluminescent device comprising the first compound with the structure of formula 1 and the second compound with the structure of formula 2 disclosed by the invention is used for the first organic layer, so that the device has excellent performance and unique advantages, especially the improvement of the efficiency and the service life of the device, provides possibility and examples for further optimization of the structure of the device, and has great wide prospect in commercial application.

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 first compound has a structure represented by formula 1:

in the formula (1) of the present invention,

r, R 'and R' are 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,sulfonyl, phosphinyloxy, substituted or unsubstituted alkyl having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having from 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having from 7 to 30 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 alkynyl 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 alkylsilyl having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having from 6 to 20 carbon atoms, and combinations thereof;

the second compound has a structure represented by formula 2:

wherein ,

X ₁ -X ₁₆ is selected identically or differently on each occurrence from C, CR _x Or N; wherein X is ₅ -X ₈ At least one of (a)One selected from C and L _x Are connected; x is X ₉ -X ₁₂ At least one of which is selected from C and is combined with L _x Are connected;

Adjacent substituent R in formula 2 _x Can optionally be linked into a ring.

2. The organic electroluminescent device of claim 1, 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, phosphinyloxy, azaaromatic ring groups, and groups selected from the group consisting of 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, phosphinyloxy, azaaryl groups: has the following characteristics ofAlkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 20 ring carbon atoms, heteroalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 30 carbon atoms, alkoxy of 1 to 20 carbon atoms, aryloxy of 6 to 30 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkynyl of 2 to 20 carbon atoms, aryl of 6 to 30 carbon atoms, heteroaryl of 3 to 30 carbon atoms, alkylsilyl of 3 to 20 carbon atoms, arylsilyl of 6 to 20 carbon atoms, and combinations thereof;

Preferably, 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.

3. The organic electroluminescent device of claim 1, wherein X and Y are, identically or differently, selected from the group consisting of:

O，S，Se，

/>

wherein ,R₂ 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 Borane, sulfinyl, sulfonyl, phosphinoxy, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted cycloalkyl having 1 to 20 carbon atomsA substituted or unsubstituted heteroalkyl having 7-30 carbon atoms, a substituted or unsubstituted alkoxy having 1-20 carbon atoms, a substituted or unsubstituted aryloxy having 6-30 carbon atoms, a substituted or unsubstituted alkenyl having 2-20 carbon atoms, a substituted or unsubstituted alkynyl having 2-20 carbon atoms, a substituted or unsubstituted aryl having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl having 6-20 carbon atoms, and combinations thereof;

wherein ,A,R_a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v and R_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 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 Substituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted alkynyl groups having 2-20 carbon atoms, substituted or unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-30 carbon atoms, substituted or unsubstituted silyl groups having 3-20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6-20 carbon atoms, and combinations thereof;

wherein A is a group having at least one electron withdrawing group, and for any of the structures, when R _a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v and R_w When one or more of them occur, R _a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v and R_w Is a group having at least one electron withdrawing group; preferably, the group having at least one 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, triazinyl, and combinations thereof;

preferably, wherein X and Y are, identically or differently, selected at each occurrence from the group consisting of:

O，S，Se，

more preferably, wherein X and Y are

4. The organic electroluminescent device of any of claims 1-3, wherein R is selected identically or differently at each occurrence from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Boranyl, sulfinyl, sulfonyl, phosphinoxy, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted alkoxy having 1 to 20 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, and is substituted by halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Any one of the following groups substituted with one or more of borane, sulfinyl, sulfonyl, and phosphinyloxy: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

Preferably, R 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, substituted with CN or CF ₃ Is substituted by one or more vinyl groups, by CN or CF ₃ One of the substituted ethynyl, dimethylphosphinyloxy, diphenylphosphinyloxy, F, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethylOxyphenyl group, bis (trifluoromethyl) phenyl group, bis (trifluoromethoxy) phenyl group, 4-cyanotetrafluorophenyl group, substituted by F, CN or CF ₃ Phenyl or biphenyl groups, tetrafluoropyridyl, pyrimidinyl, triazinyl, diphenylborane groups, oxaborolidinyl groups, and combinations thereof.

5. The organic electroluminescent device of any one of claims 1-4, wherein R is selected identically or differently at each occurrence from the group consisting of:

/>

preferably, two R are the same in one compound represented by formula 1;

wherein ,

6. The organic electroluminescent device of claim 1, wherein the first compound is selected from the group consisting of compound 1 to compound 182; the compounds 1 to 182 have a structure represented by formula 1-1:

wherein two Z structures in the formula 1-1 are the same, two R structures are the same or different, and the Z, X, Y, R groups are selected from atoms or groups shown in the following table respectively;

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7. the organic electroluminescent device of claim 1, wherein the second compound has a structure represented by formula 2-a:

wherein ,

R _x each time go outAnd wherein the times are identically or differently 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 heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl 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 alkynyl 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 alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R in formula 2-a _x Can optionally be linked into a ring.

8. The organic electroluminescent device as claimed in claim 1 or 7, wherein Ar ₁ and Ar₂ The same or different at each occurrence is selected from substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 20 carbon atoms, or combinations thereof; preferably Ar ₁ and Ar₂ Each occurrence of which is identically or differently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstitutedSubstituted quinolinyl, or a combination thereof.

9. The organic electroluminescent device as claimed in claim 1 or 7, wherein L _x Each occurrence is identically or differently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;

Preferably L _x Each occurrence is identically or differently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a combination thereof;

more preferably L _x Each occurrence is a single bond.

10. The organic electroluminescent device of claim 1, wherein the second compound has a structure represented by formula 2-c:

wherein ,

R _x and R_v ' 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 heterocyclyl having 3 to 20 ring 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 unsubstitutedUnsubstituted 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, substituted or unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

11. The organic electroluminescent device as claimed in any one of claims 1 to 10, wherein X ₁ -X ₁₆ Is selected identically or differently on each occurrence from C or CR _x； wherein ,R_x 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, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, and combinations thereof;

preferably, R _x And is selected, identically or differently, on each occurrence, from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 20 carbon atoms, and combinations thereof;

more preferably, R _x And is selected, identically or differently, on each occurrence, from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted Substituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and combinations thereof.

12. The organic electroluminescent device of claim 10, wherein R _v ' 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, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, and combinations thereof;

preferably, R _v ' is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 20 carbon atoms, and combinations thereof;

more preferably, R _v ' is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and combinations thereof.

13. The organic electroluminescent device of claim 1, wherein the second compound is selected from the group consisting of:

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14. the organic electroluminescent device of claim 1, wherein a mass ratio of the first compound to the second compound in the first organic layer ranges from 1:10000 to 10000:1;

preferably, the mass ratio of the first compound to the second compound in the first organic layer ranges from 1:1000 to 100:1;

more preferably, the mass ratio of the first compound to the second compound in the first organic layer ranges from 1:100 to 10:1.

15. The organic electroluminescent device of claim 1, further comprising a second organic layer disposed between the anode and the light-emitting layer, the second organic layer comprising a second compound.

16. The organic electroluminescent device of claim 15, further comprising a third organic layer disposed between the anode and the light-emitting layer, wherein the third organic layer comprises a different compound than the second organic layer.

17. The organic electroluminescent device of any one of claims 1-16, wherein the first organic layer is in direct contact with an anode.

18. A combination of compounds comprising a first compound and a second compound; the first compound has a structure represented by formula 1:

In the formula (1) of the present invention,

r, R 'and R' are 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 heterocyclyl having 3 to 20 ring 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 alkynyl 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, and combinations thereof;

the second compound has a structure represented by formula 2:

wherein ,

R _x 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 heterocyclyl having 3 to 20 ring 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 alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof ；

Adjacent substituent R in formula 2 _x Can optionally be linked into a ring.

19. An electronic assembly comprising the organic electroluminescent device of any one of claims 1-17.