CN117677216A

CN117677216A - Organic electroluminescent device

Info

Publication number: CN117677216A
Application number: CN202311657065.9A
Authority: CN
Inventors: 周雯庭; 刘喜庆; 韩春雪
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-12-05
Filing date: 2023-12-05
Publication date: 2024-03-08

Abstract

The invention belongs to the technical field of organic electroluminescence, and particularly relates to an organic electroluminescent device. The hole transport region of the organic electroluminescent device provided by the invention comprises at least two hole transport layers, wherein one hole transport layer contains one of the compounds shown in the formula (I), and the other hole transport layer contains one of the compounds shown in the formula (II), and by adopting the hole transport region with the layer structure, the device has proper hole transport capacity and exciton blocking capacity, and all organic functional layers can be well matched, so that the performances of driving voltage, luminous efficiency, service life and the like are well improved.

Description

Organic electroluminescent device

Technical Field

The invention belongs to the technical field of organic electroluminescence, and particularly relates to an organic electroluminescent device.

Background

An Organic Light-Emitting Diode (OLED) has the characteristics of Light and thin body, wide viewing angle, fast response speed, wide use temperature range, low energy consumption, high efficiency, good color purity, high definition, good flexibility, and the like, and has been widely used in the fields of illumination and display, and is considered as one of the display and illumination technologies with the most development prospects in the industry.

The classical OLED device is in a sandwich structure, a luminescent layer is sandwiched between two electrodes of a cathode and an anode, wherein the luminescent layer contains luminescent substances (guest materials), a certain working voltage is applied between the two electrodes, so that holes and electrons are respectively injected from the anode and the cathode and then reach the luminescent layer, excitons are generated by recombination, energy is released, the excitons migrate under the action of an electric field, energy is transferred to the luminescent substances, electrons in molecules of the luminescent substances migrate from a ground state to an excited state, and the electrons migrate from the excited state to the ground state again due to unstable excited states, thereby releasing the energy in the form of light and generating a luminescence phenomenon. In order to improve the driving voltage, luminous efficiency, color purity, definition, and service life of the device, a hole transport region is generally disposed between the anode and the light emitting layer, and an electron transport region is disposed between the cathode and the light emitting layer. The hole transport region mainly plays a role in injecting and transporting holes and can comprise more than one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, an electron blocking layer and the like; the electron transport region mainly plays a role in injecting and transporting electrons, and may include one or more of an electron injection layer, an electron transport layer, a hole blocking layer, and the like. Meanwhile, the organic layers in the two charge transmission areas and the organic layers with other functions (such as a luminescent layer) are required to have good energy level matching, so that excitons are prevented from diffusing to the edge of the luminescent layer, and effective luminescence in the luminescent layer with high ratio is maintained, thus not only improving the luminous efficiency of the device, but also avoiding rapid aging of organic materials because of reducing the heat generated by interface luminescence, and further prolonging the service life of the device. In addition to the organic functional layer between the anode and the cathode, a coating layer having a high refractive index and high light transmittance is provided on the outer side of the light-emitting side electrode (for example, the outer side of the cathode of the top-emission device), thereby improving the light-emitting efficiency and color purity of the device.

At present, most of OLED devices used in industry have a defect of mismatch of hole and electron transmission rates, which results in degradation of performance such as driving voltage, luminous efficiency and service life of the device, so OLED workers are required to continuously optimize and innovate materials selected for OLED and OLED device structure.

Disclosure of Invention

In order to solve the technical problems, the invention provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer, wherein the organic layer is arranged between the anode and the cathode, the organic layer comprises a hole transmission area, a luminescent layer and an electron transmission area, the hole transmission area comprises at least two layers of hole transmission layers, one layer of hole transmission layer contains one of compounds shown in a formula (I), the other layer of hole transmission layer contains one of compounds shown in a formula (II), the organic functional layers formed by the two materials can well match the transmission rates of holes and electrons, meanwhile, the energy level matching degree between the functional layers is also high, the driving voltage of the device can be effectively reduced, the luminous efficiency of the device is improved, and the service life of the device is prolonged:

in formula (I), the Ar ₁ 、Ar ₂ Independently selected from one of the structures shown below:

wherein, a is as follows ₁ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₁ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₁ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4 or 5;

said R is ₁ 、R ₂ Independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or substituted C1 to C12 alkyl group;

said R is ₃ And is selected, identically or differently, for each occurrence, from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring, and a C3-C7 lipidOne of the groups formed by ring fusion, two adjacent R ₃ Can be linked to form one of a substituted or unsubstituted C3-C7 aliphatic ring and a substituted or unsubstituted C6-C10 aromatic ring;

ar as described ₃ One selected from the group consisting of a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 aliphatic ring;

The L is ₁ ～L ₃ Independently selected from one of single bond, substituted or unsubstituted arylene of C6-C30, and divalent group formed by fusing substituted or unsubstituted aromatic ring of C6-C30 and aliphatic ring of C3-C7;

in formula (II), the Ar ₁₀₁ One selected from the following structures:

wherein, a is as follows ₁₀₁ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₁₀₁ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₁₀₁ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4 or 5;

said R is ₁₀₁ 、R ₁₀₂ Independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or substituted C1 to C12 alkyl group;

said R is ₁₀₃ Each occurrence is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or substituted C3-C10 cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 alicyclic ring, and two adjacent R ₁₀₃ Can be linked to form one of a substituted or unsubstituted C3-C7 aliphatic ring and a substituted or unsubstituted C6-C10 aromatic ring;

Ar as described ₁₀₂ Selected from the followingOne of the structures is shown:

wherein X is selected from oxygen atom or sulfur atom;

the a ₁₀₂ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₁₀₂ Each occurrence is identically or differently selected from 0, 1, 2 or 3;

said R is ₁₀₄ Each occurrence is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or substituted C3-C10 cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 alicyclic ring, and two adjacent R ₁₀₄ Can be linked to form one of a substituted or unsubstituted C3-C7 aliphatic ring and a substituted or unsubstituted C6-C10 aromatic ring;

ar as described ₁₀₃ One selected from the group consisting of a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 aliphatic ring;

the L is ₁₀₁ ～L ₁₀₃ Independently selected from one of single bond, substituted or unsubstituted arylene of C6-C30, and divalent group formed by fusing substituted or unsubstituted aromatic ring of C6-C30 and aliphatic ring of C3-C7.

The beneficial effects are that:

the hole transport region of the organic electroluminescent device provided by the invention comprises at least two hole transport layers, wherein one hole transport layer contains one of the compounds shown in the formula (I), and the other hole transport layer contains one of the compounds shown in the formula (II), and by adopting the hole transport region with the layer structure, the device has proper hole transport capacity and exciton blocking capacity, and all organic functional layers can be well matched, so that the performances of driving voltage, luminous efficiency, service life and the like are well improved.

Detailed Description

The following description of the embodiments of the present invention will be made more complete and obvious by the following description of the embodiments of the present invention, wherein the embodiments are described in some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.

In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance. Taking hydrogen as an example, each hydrogen atom of all naturally occurring compounds contains about 0.0156 atomic% deuterium.

In the present invention, the use of "H" and "hydrogen atom" means that the hydrogen atom in the chemical structure contains no more than the natural abundance of deuterium or tritium atoms, for example, no more than 0.0156 atomic% deuterium. "D" and "deuterium atom" refer to any value having an abundance of deuterium content above natural abundance, e.g., above 0.1 atom%, above 1 atom%, above 10 atom%, e.g., where about 95 atom% is deuterium. "T" and "tritium atom" refer to any value where the abundance of tritium content is above natural abundance, e.g., greater than 0.1 atomic%, greater than 1 atomic%, greater than 10 atomic%, e.g., where about 95% is tritium. In the present invention, hydrogen not shown is omitted to indicate "H" or "hydrogen atom".

The halogen atom in the present invention means fluorine atom, chlorine atom, bromine atom and iodine atom.

As used herein, "silyl" refers to-SiH ₃ A group, the "substituted or unsubstituted silyl" refers to one or more H on the silyl group being substituted or unsubstituted with a substituent. The "substituted or unsubstituted silyl group" may be represented by-Si (R _k ) ₃ A representation, wherein each R _k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted Alkyl of C1-C30, alkenyl of substituted or unsubstituted C1-C30, cycloalkyl of substituted or unsubstituted C3-C30, aryl of substituted or unsubstituted C6-C60, heteroaryl of substituted or unsubstituted C2-C60, fused ring group of alicyclic ring of substituted or unsubstituted C3-C30 and aromatic ring of C6-C60, fused ring group of alicyclic ring of substituted or unsubstituted C3-C30 and heteroaromatic ring of C2-C60. Preferably, each R _k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl. The number of carbon atoms of the alkyl group is preferably 1 to 20, preferably 1 to 15, more preferably 1 to 10, and most preferably 1 to 8. The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, preferably 3 to 15, more preferably 3 to 10, and most preferably 3 to 7. The number of carbon atoms of the aryl group is preferably 6 to 20, preferably 6 to 13, more preferably 6 to 12, and most preferably 6 to 10. Preferably, each R _k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl. Preferred substituted silyl groups include, but are not limited to, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like. The above-mentioned substituted silyl group is preferably trimethylsilyl group, triethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, phenyldimethylsilyl group, diphenylmethylsilyl group, phenyldiphenyldisilyl group Methylsilyl groups.

The alkyl group according to the present invention is a hydrocarbon group having at least one hydrogen atom in the alkane molecule, and may be a straight chain alkyl group or a branched chain alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight-chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, an isomeric group of n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, or an n-hexyl group.

Cycloalkyl according to the invention is a hydrocarbon radical formed by the removal of at least one hydrogen atom from a cyclic alkane molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 5 to 10 carbon atoms. Examples may include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, and the like. The cycloalkyl group is preferably a cyclopentylalkyl group, a cyclohexenyl group, a 1-adamantyl group, a 2-adamantyl group, or a norbornyl group.

Cycloalkenyl according to the invention means hydrocarbon radicals formed by the removal of at least one hydrogen atom from the cycloolefin molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 5 to 10 carbon atoms. Examples may include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and the like. The cycloalkyl group is preferably a cyclopentenyl group or a cyclohexenyl group.

The heterocycloalkyl group according to the present invention is a group formed by dropping at least one hydrogen atom from a heterocyclic molecule having at least one heteroatom other than carbon atoms, and the heteroatom includes a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a selenium atom, a phosphorus atom, and the like, and is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. Preferably from 1 to 3 heteroatoms, more preferably from 1 to 2 heteroatoms, particularly preferably 1 heteroatom. Preferably from 3 to 15, more preferably from 3 to 12, particularly preferably from 5 to 6, ring atoms. Examples may include, but are not limited to, oxiranyl, ethylidenyl, tetrahydropyrrolyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, and the like. The heterocyclic group is preferably a tetrahydropyrrolyl group, a piperidyl group, a morpholinyl group, a thiomorpholinyl group, or a piperazinyl group.

Aryl in the present invention means that after one hydrogen atom is removed from the aromatic nucleus carbon of the aromatic compound molecule, a monovalent group is left, which may be a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, or a condensed group of an aryl group and an alicyclic ring, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, for example, phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, etc., but is not limited thereto; the condensed ring aryl group refers to an aryl group having two or more aromatic rings in the molecule and condensed by sharing two adjacent carbon atoms with each other, for example, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthryl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, spiro-cyclopentyl-fluorenyl, spiro-cyclohexyl-fluorenyl, spiro-adamantyl-fluorenyl, spiro-cyclopentenyl-fluorenyl, spiro-cyclohexenyl-fluorenyl, and the like, but is not limited thereto. The aryl group is preferably phenyl, biphenyl, terphenyl, 1-naphthyl, 2-naphthyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, spiro-cyclopentyl-fluorenyl, spiro-cyclohexyl-fluorenyl, spiro-adamantyl-fluorenyl, spiro-cyclopentenyl-fluorenyl, spiro-cyclohexenyl-fluorenyl.

Heteroaryl according to the present invention refers to the generic term for groups in which one or more aromatic nucleus carbon atoms in the aryl group are replaced by heteroatoms, including but not limited to oxygen, sulfur, nitrogen, silicon, selenium or phosphorus atoms, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, most preferably 3 to 12 carbon atoms, the attachment site of the heteroaryl group may be located on a ring-forming carbon atom, or on a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroaryl group includes, but is not limited to, quinolinyl, isoquinolinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiazinyl, and the like. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a benzodibenzothienyl group, a benzodibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenoxathiazide group.

The group formed by fusing the aromatic ring and the aliphatic ring refers to the general name that after the aromatic ring and the aliphatic ring (cycloalkyl, cycloalkenyl and cycloalkynyl) are fused together, one hydrogen atom is removed, and a monovalent group is left. The aromatic ring preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms, which may include benzene, naphthalene, anthracene, phenanthrene, etc., but is not limited thereto; the alicyclic ring preferably has 3 to 9 carbon atoms, more preferably 5 to 7 carbon atoms, which may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclopropyne, cyclobutyne, cyclopentyne, cyclohexayne, cycloheptyne. Preferably, examples of the group in which the aromatic ring is condensed with the aliphatic ring may include, but are not limited to, benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocycloheptyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptenyl, naphthocyclopropyl, naphthocyclobutyl, naphthocyclopentyl, naphthocyclohexyl, and the like.

Arylene in the context of the present invention means an aryl group having two bonding sites, i.e., a divalent group. With respect to the description of aryl groups that may be applied, provided above, the difference is that arylene groups are divalent groups.

Heteroaryl, as used herein, means a heteroaryl group having two bonding sites, i.e., a divalent group. With respect to the description of heteroaryl groups that may be applied, provided above, the difference is that the heteroarylene group is a divalent group.

The divalent group formed by fusing an aromatic ring and an aliphatic ring in the present invention refers to a group formed by fusing an aromatic ring and an aliphatic ring having two bonding sites, that is, a divalent group. Regarding the description thereof, which can be applied to the group formed by fusing an aromatic ring and an aliphatic ring provided above, the difference is that a divalent group formed by fusing an aromatic ring and an aliphatic ring is a divalent group.

"substitution" as used herein means that a hydrogen atom in some of the functional groups is replaced with another atom or functional group (i.e., substituent), and the position of substitution is not limited as long as the position is one where a hydrogen atom is substituted, and when two or more are substituted, two or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" as used herein means that it is not substituted or substituted with one or more substituents selected from the group consisting of: deuterium atom, halogen atom, amino group, cyano group, nitro group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C3-C30 cycloalkenyl group, substituted or unsubstituted C3-C30 heterocycloalkyl group, substituted or unsubstituted C6-C60 aryl group, substituted or unsubstituted C6-C60 aryloxy group, substituted or unsubstituted C2-C60 heteroaryl group, substituted or unsubstituted silyl group, preferably deuterium atom, halogen atom, cyano group, nitro group, C1-C12 alkyl group, C3-C12 cycloalkyl group, C3-C12 cycloalkenyl group, C3-C12 heterocycloalkyl group, C6-C30 aryl group, C3-C30 heteroaryl group, substituted or unsubstituted silyl group, in the case of being substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other; preferably, it means not substituted or substituted with one or more substituents selected from the group consisting of: deuterium atoms, fluorine atoms, cyano groups, methyl groups, trifluoromethyl groups, deuteromethyl groups, ethyl groups, deuteroethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, deuterated tert-butyl groups, n-pentyl groups, n-hexyl groups, cyclopropane groups, methyl-substituted cyclopropane groups, ethyl-substituted cyclopropane groups, deuterated cyclopropane groups, cyclobutane groups, methyl-substituted cyclobutane groups, ethyl-substituted cyclobutane groups, deuterated cyclobutane groups, cyclopentane groups, methyl-substituted cyclopentane groups, ethyl-substituted cyclopentane groups, deuterated cyclopentane groups, cyclohexane groups, methyl-substituted cyclohexane groups, ethyl-substituted cyclohexane groups, n-propyl-substituted cyclohexane groups, n-butyl-substituted cyclohexane groups, deuterated cyclohexane groups, cycloheptane groups, cyclopentene groups, methyl-substituted cyclopentene groups ethyl substituted cyclopentenyl, cyclohexenyl, cycloheptenyl, adamantyl, methyl substituted adamantyl, ethyl substituted adamantyl, deuterated adamantyl, norbornyl, methyl substituted norbornyl, ethyl substituted norbornyl, deuterated norbornyl, tetrahydropyrrolyl, piperidinyl, morpholinyl, thiomorpholinyl, methyl substituted piperazinyl, ethyl substituted piperazinyl, phenyl substituted piperazinyl, naphthyl substituted piperazinyl, phenyl, deuterophenyl, naphthyl, deuteroalkenyl, anthracenyl, deuteroalkanyl, phenanthryl, deuterophenyl, triphenylenyl, pyrenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, spiro-cyclopentyl-fluorenyl, spiro-cyclohexyl-fluorenyl, spiro-adamantyl-fluorenyl, spiro-cyclopentenyl-fluorenyl, spiro-cyclohexenyl-fluorenyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, N-phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, trimethylsilyl, triphenylsilyl, where substituted with multiple substituents, the multiple substituents may be the same or different from each other.

In this specification, when the position of a substituent or attachment site on a ring is not fixed, it means that it can be attached to any of the optional sites of the ring. For example, the number of the cells to be processed,can indicate-> Can represent Can indicate-> And so on.

In this specification, when a substituent or linkage site is located across two or more rings, it is meant that it may be attached to either of the two or two rings, in particular to either of the respective selectable sites of the rings. For example, the number of the cells to be processed,can indicate-> Can indicate->Can indicate->And so on.

The linking to form a ring structure (e.g., to form a saturated or unsaturated C3-C10 carbocycle, to form a substituted or unsubstituted saturated or unsaturated C3-C6 carbocycle) as described herein means that the individual groups are linked to each other by chemical bonds and optionally form double/triple bonds, and may constitute aromatic groups, as exemplified below:

in the present invention, the ring formed by the connection may be an aromatic ring system, an aliphatic ring system or a ring system formed by the fusion of both, and the ring formed by the connection may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a spiro ring or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentaacene, cyclohexene, cyclohexane acene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

In the present specification, "at least one" includes one, two, three, four, five, six, seven, eight, or more.

A layer described herein as being "on" another layer or electrode may be construed as directly on the other layer or electrode, or may have other layer structures in between.

A layer described herein as being "between" two layers, two electrodes, or one layer and an electrode may be interpreted as the only layer structure between the two, or one or more layer structures may exist between the two.

The invention provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode, the organic layer comprises a hole transmission area, a light-emitting layer and an electron transmission area, the hole transmission area comprises at least two hole transmission layers, one hole transmission layer contains one of compounds shown as a formula (I), and the other hole transmission layer contains one of compounds shown as a formula (II):

said R is ₃ Each occurrence is the same or different and is selected from one of hydrogen atom, deuterium atom, halogen atom, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl and C3-C7 alicyclic fused, adjacent two R ₃ Can be linked to form one of a substituted or unsubstituted C3-C7 aliphatic ring and a substituted or unsubstituted C6-C10 aromatic ring;

ar as described ₃ Selected from substituted or unsubstituted C6-C30Aryl, one of the groups formed by fusing a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 aliphatic ring;

In formula (II), the Ar ₁₀₁ One selected from the following structures:

ar as described ₁₀₂ One selected from the following structures:

wherein X is selected from oxygen atom or sulfur atom;

Preferably, said R ₁ 、R ₂ And is selected from one of methyl, deuterated methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, deuterated tert-butyl, n-pentyl and n-hexyl.

Preferably, said R ₃ And is selected from, identically or differently, one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a deuterated tert-butyl group, an n-pentyl group, an n-hexyl group, an adamantyl group, a norbornyl group, a trimethylsilyl group, a triphenylsilyl group, a phenyl group, a deuterated phenyl group.

Preferably, said Ar ₁ 、Ar ₂ Independently selected from one of the structures shown below:

wherein, a is as follows ₃₁ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₃₁ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₃₁ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4 or 5; d is as follows ₃₁ Each occurrence is identically or differently selected from 0, 1 or 2;

said R is ₃₁ And is selected from, identically or differently, one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a deuterated tert-butyl group, an n-pentyl group, an n-hexyl group, an adamantyl group, a norbornyl group, a trimethylsilyl group, a triphenylsilyl group, a phenyl group, a deuterated phenyl group.

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preferably, said Ar ₃ One selected from the following structures:

wherein, a is as follows ₄ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4 or 5; said b ₄ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; the said c ₄ Each occurrence is identically or differently selected from 0, 1, 2 or 3; d is as follows ₄ Each occurrence is identically or differently selected from 0, 1 or 2; said e ₄ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5 or 6; said f ₄ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

said R is ₄ Each occurrence of which is the same or different and is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or substituted C3-C10 cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 aliphatic ring;

said R is ₅ And is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, identically or differently at each occurrence.

Preferably, said R ₄ And is selected from, identically or differently, one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a deuterated tert-butyl group, an n-pentyl group, an n-hexyl group, an adamantyl group, a norbornyl group, a trimethylsilyl group, a triphenylsilyl group, a phenyl group, a deuterated phenyl group.

Preferably, said R ₅ And is selected from one of hydrogen atom, deuterium atom, fluorine atom, cyano group, methyl group, deuterated methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group and deuterated tert-butyl group.

Preferably, said Ar ₃ One selected from the following structures:

preferably, said L ₁ ～L ₃ Independently selected from a single bond or one of the structures shown below:

wherein, a is as follows ₆ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₆ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₆ Each occurrence is identically or differently selected from 0, 1 or 2; d is as follows ₆ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5 or 6; said e ₆ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

said R is ₆ Each occurrence of which is the same or different and is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or substituted C3-C10 cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 aliphatic ring;

said R is ₇ And is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, identically or differently at each occurrence.

Preferably, said R ₆ And is selected from one of hydrogen atom, deuterium atom, fluorine atom, cyano group, methyl group, deuterated methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, deuterated tert-butyl group, trimethylsilyl group, phenyl group, deuterated phenyl group.

Preferably, said R ₇ Is selected from the group consisting of hydrogen, deuterium, fluorine, cyano, methyl, deuteromethyl, ethyl, n-propyl, isopropyl, and the like, identically or differently at each occurrence, One of n-butyl, sec-butyl, isobutyl, tert-butyl, deuterated tert-butyl.

preferably, said Ar ₁₀₁ One selected from the following structures:

wherein, a is as follows ₂₀₃ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₂₀₃ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₂₀₃ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4 or 5; d is as follows ₂₀₃ Each occurrence is identically or differently selected from 0, 1 or 2;

said R is ₂₀₃ And is selected from, identically or differently, one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a deuterated tert-butyl group, an n-pentyl group, an n-hexyl group, an adamantyl group, a norbornyl group, a trimethylsilyl group, a triphenylsilyl group, a phenyl group, a deuterated phenyl group.

Preferably, said Ar ₁₀₁ One selected from the following structures:

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preferably, said Ar ₁₀₂ One selected from the following structures:

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wherein, a is as follows ₂₀₄ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₂₀₄ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₂₀₄ Each occurrence is identically or differently selected from 0, 1 or 2;

said R is ₂₀₄ And is selected from, identically or differently, one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a deuterated tert-butyl group, an n-pentyl group, an n-hexyl group, an adamantyl group, a norbornyl group, a trimethylsilyl group, a triphenylsilyl group, a phenyl group, a deuterated phenyl group.

Preferably, said Ar ₁₀₂ One selected from the following structures:

preferably, said Ar ₁₀₃ One selected from the following structures:

wherein, a is as follows ₂₀₅ Each occurrence of which is the same or differentFrom 0, 1, 2, 3, 4 or 5; said b ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; the said c ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2 or 3; d is as follows ₂₀₅ Each occurrence is identically or differently selected from 0, 1 or 2; said e ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5 or 6; said f ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

said R is ₂₀₅ Each occurrence of which is the same or different and is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or substituted C3-C10 cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 aliphatic ring;

said R is ₂₀₆ And is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, identically or differently at each occurrence.

Preferably, said R ₂₀₅ And is selected from, identically or differently, one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a methyl group, a deuterated methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a deuterated tert-butyl group, an n-pentyl group, an n-hexyl group, an adamantyl group, a norbornyl group, a trimethylsilyl group, a triphenylsilyl group, a phenyl group, a deuterated phenyl group.

Preferably, said R ₂₀₆ And is selected from one of hydrogen atom, deuterium atom, fluorine atom, cyano group, methyl group, deuterated methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group and deuterated tert-butyl group.

Preferably, said Ar ₁₀₃ One selected from the following structures:

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preferably, said L ₁₀₁ ～L ₁₀₃ Independently selected from a single bond or one of the structures shown below:

wherein, a is as follows ₁₀₇ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₁₀₇ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₁₀₇ Each occurrence is identically or differently selected from 0, 1 or 2; d is as follows ₁₀₇ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5 or 6; said e ₁₀₇ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

said R is ₁₀₇ Each occurrence of which is the same or different and is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or substituted C3-C10 cycloalkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aromatic ring and a C3-C7 aliphatic ring;

said R is ₁₀₈ And is selected from one of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, identically or differently at each occurrence.

Preferably, said R ₁₀₇ And is selected from one of hydrogen atom, deuterium atom, fluorine atom, cyano group, methyl group, deuterated methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, deuterated tert-butyl group, trimethylsilyl group, phenyl group, deuterated phenyl group.

Preferably, said R ₁₀₈ And is selected from one of hydrogen atom, deuterium atom, fluorine atom, cyano group, methyl group, deuterated methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group and deuterated tert-butyl group.

Preferably, said L ₁₀₂ ～L ₁₀₃ Independently selected from a single bond or one of the structures shown below:

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preferably, the compound shown in the formula (I) is selected from one of the compounds shown in the following formulas (I-A) to (I-F):

wherein Ar is as described ₃ 、L ₁ ～L ₃ 、a ₁ 、b ₁ 、c ₁ 、R ₁ 、R ₂ 、R ₃ All as described herein.

Preferably, the compound shown in the formula (I) is selected from one of the following compounds:

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preferably, the compound shown in the formula (II) is selected from one of the compounds shown in the following formulas (II-A) to (II-C):

wherein Ar is as described ₁₀₃ 、R ₁₀₁ ～R ₁₀₄ 、X、L ₁₀₁ ～L ₁₀₃ 、a ₁₀₁ 、b ₁₀₁ 、c ₁₀₁ 、a ₁₀₂ 、b ₁₀₂ All as described herein. Preferably, the compound shown in the formula (II) is selected from one of the following compounds:

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The organic electroluminescent device comprises an anode, a hole transport region above the anode, a luminescent layer above the hole transport region, an electron transport region above the luminescent layer, and a cathode above the electron transport region.

The organic electroluminescent device according to the present invention may further comprise a capping layer over the cathode.

The anode of the invention can be a reflective anode, such as a reflective film formed by silver (Ag), magnesium (Mg), aluminum (Al), gold (Au), nickel (Ni), chromium (Cr), ytterbium (Yb) or alloys thereof, or a transparent or semitransparent layer structure with high work function, such as Indium Tin Oxide (ITO), indium zinc oxide (ZnO), aluminum Zinc Oxide (AZO), indium Gallium Oxide (IGO), indium oxide (In) ₂ O ₃ ) Or tin oxide (SnO) ₂ ) The layer structure is formed according to the type of the device to be manufactured, if the device to be manufactured is a bottom emission device (anode side emits light), a transparent or semitransparent anode is required to be manufactured, and if the device to be manufactured is a top emission device (cathode side emits light), a reflecting anode is required to be manufactured.

The hole transport region comprises more than one organic functional layer of a hole injection layer, a hole transport layer and a light-emitting auxiliary layer.

The hole injection layer of the present invention may have a single-layer structure formed of a single material, or may have a single-layer structure or a multi-layer structure formed of different materials. Examples of the compounds include, but are not limited to, triarylamines, porphyrins, styrenes, polythiophenes and derivatives thereof, phthalocyanine derivatives, axial olefins, and other compounds having high hole injection properties, for example, 4' -tris [ 2-naphthylphenylamino ] triphenylamine (2-TNATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazabenzophenanthrene (HATCN), copper phthalocyanine (CuPC), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethylbenzoquinone (F4-TCNQ), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT/PSS), compounds HT-1 to HT-11, compounds p-1 to p-3, compounds represented by the formula (I) of the present invention, and compounds represented by the formula (II) of the present invention.

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Preferably, the hole injection layer has a single layer structure of a single substance, and the substance may be 2 to TNATA, HATCN, cuPC.

Preferably, the hole injection layer has a single-layer structure composed of different substances. More preferably, the hole injection layer has a single-layer structure composed of two substances, one is a triarylamine compound, for example, compounds HT-1 to HT-11, a compound represented by formula (I) of the present invention, a compound represented by formula (II) of the present invention, and the other is an axylene compound or other substance having high hole injection properties, for example, HATCN, F4-TCNQ, and compounds p-1 to p-3.

The hole transport layer of the present invention may have a single layer structure of a single material, or may have a single layer structure or a multilayer structure of different materials. Triarylamine compounds can be used, as can other hole mobilities at 10 ^-6 cm ² Examples of the substances above/Vs include, but are not limited to, N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4' -tris (N, N-diphenylamino) triphenylamine (TDATA), the above-mentioned compounds HT-1 to HT-11, the compound represented by the formula (I) of the present invention, and the compound represented by the formula (II) of the present invention.

Preferably, the hole transport layer has a single layer structure formed of a single substance, and the substance is a compound represented by formula (I).

Preferably, the hole transport layer has a single layer structure formed of a single substance, and the substance is a compound represented by formula (II).

Preferably, the hole transport layer has a single layer structure formed of different substances, wherein the different substances are selected from the compounds shown in the formula (I), and each substance is a different compound. More preferably, the hole transport layer has a single layer structure formed of two substances, wherein the two substances are selected from the compounds shown in the formula (I), and the two substances are different compounds.

Preferably, the hole transport layer has a single layer structure formed of different substances, wherein the different substances are selected from the compounds shown in the formula (II), and each substance is a different compound. More preferably, the hole transport layer has a single layer structure formed of two substances, wherein the two substances are selected from the compounds shown in formula (II), and the two substances are different compounds.

Preferably, the hole transport layer is a multi-layer structure formed by different substances, wherein the different substances are selected from compounds shown in a formula (I), and each substance is a different compound. More preferably, the hole transport layer is a bilayer structure formed of two substances, wherein the two substances are selected from the compounds shown in formula (I), and the two substances are different compounds. Further preferably, the hole transport layer is a bilayer structure formed of two substances, wherein the two substances are selected from the compounds shown in formula (I), and the two substances are different compounds, and each layer structure contains only one substance.

Preferably, the hole transport layer is a multi-layer structure formed of different substances, wherein the different substances are selected from the compounds shown in the formula (II), and each substance is a different compound. More preferably, the hole transport layer is a double-layer structure composed of two substances, wherein the two substances are selected from the compounds shown in the formula (II), and the two substances are different compounds. Further preferably, the hole transport layer is a double-layer structure composed of two substances, wherein the two substances are selected from the compounds shown in the formula (II), and the two substances are different compounds, and each layer structure contains only one substance.

The light-emitting auxiliary layer of the present invention may have a single-layer structure composed of a single substance, or may have a single-layer structure or a multi-layer structure composed of different substances. Examples of the compounds include, but are not limited to, N- ([ 1,1' -diphenyl ] -4-yl) -N- (9, 9-dimethyl-9H-furan-2-yl) -9,9' -spirobifluorene-2-amine, N-di ([ 1,1' -biphenyl ] -4-yl) -3' - (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine, the following compounds HT-12 to HT-23, the present compounds represented by formula (I), and the present compounds represented by formula (II).

Preferably, the hole transport region includes two hole transport layers (a first hole transport layer and a second hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, the first hole transport layer is of a single-layer structure formed by a single substance selected from compounds shown in a formula (I), and the second hole transport layer is of a single-layer structure formed by a single substance selected from compounds shown in a formula (II).

Preferably, the hole transport region includes two hole transport layers (a first hole transport layer and a second hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, the first hole transport layer is of a single-layer structure formed by a single substance selected from compounds shown in a formula (II), and the second hole transport layer is of a single-layer structure formed by a single substance selected from compounds shown in a formula (I).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the second hole transport layer is a single layer structure formed by a single substance, wherein the substance is not selected from the compounds shown in the formula (I) and the compounds shown in the formula (II); the third hole transport layer is a single layer structure composed of a single substance selected from the group consisting of compounds represented by formula (II).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (II); the second hole transport layer is a single layer structure formed by a single substance, wherein the substance is not selected from the compounds shown in the formula (I) and the compounds shown in the formula (II); the third hole transport layer is a single layer structure formed by a single substance selected from the compounds shown in the formula (I).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance, wherein the substance is not selected from the compounds shown in the formula (I) and the compounds shown in the formula (II); the second hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the third hole transport layer is a single layer structure composed of a single substance selected from the group consisting of compounds represented by formula (II).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance, wherein the substance is not selected from the compounds shown in the formula (I) and the compounds shown in the formula (II); the second hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (II); the third hole transport layer is a single layer structure formed by a single substance selected from the compounds shown in the formula (I).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The second hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the second hole transport layer is a single layer structure formed by a single substance, wherein the substance is not selected from the compounds shown in the formula (I) and the compounds shown in the formula (II); the third hole transport layer is a single layer structure composed of a single substance selected from the group consisting of compounds represented by formula (II).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the second hole transport layer is a single layer structure formed by a single substance, wherein the substance is selected from compounds shown in a formula (I) and is different from the compounds in the first hole transport layer; the third hole transport layer is a single layer structure composed of a single substance selected from the group consisting of compounds represented by formula (II).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the second hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (II); the third hole transport layer has a single layer structure formed of a single substance selected from the group consisting of the compounds represented by the formula (I) and different from the compounds in the first hole transport layer.

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (II); the second hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the third hole transport layer has a single layer structure formed of a single substance selected from the group consisting of the compounds represented by the formula (I) and different from the compounds in the second hole transport layer.

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (II); the second hole transport layer is a single layer structure formed by a single substance selected from the compounds shown in the formula (II) and different from the compounds in the first hole transport layer; the third hole transport layer is a single layer structure formed by a single substance selected from the compounds shown in the formula (I).

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (II); the second hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the third hole transport layer has a single layer structure formed of a single substance selected from the group consisting of the compounds represented by the formula (II) and different from the compounds in the first hole transport layer.

Preferably, the hole transport region includes three hole transport layers (a first hole transport layer, a second hole transport layer, and a third hole transport layer): the first hole transport layer is positioned between the anode and the light-emitting layer, the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer, and the third hole transport layer is positioned between the second hole transport layer and the light-emitting layer. The first hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (I); the second hole transport layer is a single layer structure formed by a single substance selected from compounds shown in a formula (II); the third hole transport layer has a single layer structure formed of a single substance selected from the group consisting of the compounds represented by the formula (II) and different from the compounds in the second hole transport layer.

The light emitting layer according to the present invention includes a guest material and a host material, and a dual host material formed of two host materials may be used. The guest material may use fluorescent compoundFor example, pyrene derivatives, fluoranthene derivatives, aromatic amine derivatives, etc., and examples thereof include 10- (2-benzothiazolyl) -2,3,6, 7-tetrahydro-1, 7-tetramethyl-1H, 5H,11H- [1 ]]Benzopyran [6,7,8-ij ]]Quinolizin-11-one (C545T), 4' -bis (9-ethyl-3-carbazolyl vinyl) -1,1' -biphenyl (BCzVBi), 4' -bis [4- (di-p-tolylamino) styryl]Examples of the metal complex such as an iridium complex, an osmium complex, and a platinum complex, which may be used as a phosphorescent light-emitting material, include bis (4, 6-difluorophenylpyridine-N, C2) picolinated iridium (FIrpic) and tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) ₂ (acac)) and the like. The host material is preferably a material having higher LUMO and lower HOMO than the guest material, for example, a metal complex such as an aluminum complex or zinc complex, an oxadiazole derivative, a benzoxazole derivative, a heterocyclic compound such as a benzothiazole derivative or a benzimidazole derivative, a condensed aromatic compound such as a carbazole derivative or an anthracene derivative, an aromatic amine compound such as a triarylamine derivative or a condensed polycyclic aromatic amine derivative, and examples thereof include Alq ₃ BAlq, TPBI, TPD, 4 '-bis (9-Carbazolyl) Biphenyl (CBP), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (2-naphthyl) Anthracene (ADN), but are not limited thereto.

The electron transport region according to the present invention includes at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.

The electron injection layer of the invention can be a single layer structure formed by a single substance, can also be a single layer structure or a multi-layer structure formed by different substances, and can be selected from one or more of the following substances: alkali metal, alkaline earth metal, alkali metal halide, alkaline earth metal halide, alkali metal oxide, alkaline earth metal oxide, alkali metal salt, alkaline earth metal salt, and other substances having high electron injection properties. Examples can be cited as Li, ca, sr, liF, csF, caF ₂ 、BaO、Li ₂ CO ₃ 、CaCO ₃ 、Li ₂ C ₂ O ₄ 、Cs ₂ C ₂ O ₄ 、CsAlF ₄ LiOx, yb, tb, etc., but is not limited thereto.

The electron transporting layer according to the present invention may have a single layer structure, or may have a single layer structure or a multilayer structure of different materials, and aluminum complex, lithium complex, beryllium complex, zinc complex, oxazole derivative, benzoxazole derivative, thiazole derivative, benzothiazole derivative, imidazole derivative, benzimidazole derivative, carbazole derivative, phenanthroline derivative, polymer compound, etc. having high electron transporting property may be used, and examples thereof include 8-hydroxyquinoline aluminum (Alq ₃ ) Bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (BeBq ₂ ) Bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1, 1' -biphenyl-4-hydroxy) aluminum (BAlq), 2- (4-biphenyl) -5-Phenyloxadiazole (PBD), but is not limited thereto.

The hole blocking layer of the present invention may have a single layer structure formed of a single material, or may have a single layer structure or a multilayer structure formed of different materials. The material selected requires a T1 energy level higher than the light emitting layer so that energy loss from the light emitting layer is blocked. In addition, the HOMO energy level of the selected material is lower than that of the main body material of the light-emitting layer, so that the hole blocking effect is realized. Further, the electron mobility of the hole blocking layer material used was 10 ^-6 cm ² and/Vs, facilitating electron transport. One or more of the following may be selected: aluminum complex, lithium complex, beryllium complex, oxazole derivative, benzoxazole derivative, thiazole derivative, benzothiazole derivative, imidazole derivative, benzimidazole derivative, phenanthroline derivative, polymer compound, and the like. Examples include, but are not limited to, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), BAlq, and the like.

The cathode of the invention can be a thin film with low work function, which is made of lithium, calcium, lithium fluoride/aluminum, silver, magnesium silver alloy, etc., and can be made into a reflecting electrode, a transparent electrode or a semitransparent electrode by adjusting the thickness of the film, if a bottom emission device is required to be prepared, a reflecting cathode is required to be prepared, if a top emission device is required to be prepared, and a transparent or semitransparent cathode is required to be prepared.

The coating layer according to the invention may be a single substanceThe single-layer structure may be a single-layer structure or a multi-layer structure of different materials. The material for the covering layer may be an organic or inorganic substance having an appropriate refractive index, and may be, for example, a metal halide, oxide, nitride, oxynitride, sulfide, selenide, aromatic hydrocarbon compound, heteroaromatic compound, aromatic amine compound, or the like, and LiF, csF, mgF is exemplified ₂ 、CaF ₂ 、CsCl、CuI、V ₂ O ₅ 、WO ₃ 、MoO ₃ 、TiO ₂ 、ZrO、ZnO、SiO ₂ 、SiN、ZnS、Alq ₃ The compound HT-1, the compound HT-10, the compound CP-1 and the compound CP-2 are not limited thereto.

Preferably, the structure of the organic electroluminescent device is one of the following device structures:

1) An anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

2) An anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a light emitting auxiliary layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

3) An anode/a hole injection layer/a first hole transport layer/a light emitting auxiliary layer/a second hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

4) Anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

5) An anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a light emitting auxiliary layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;

6) An anode/a hole injection layer/a first hole transport layer/a light emitting auxiliary layer/a second hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;

7) An anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a third hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

8) An anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a third hole transport layer/a light emitting auxiliary layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

9) An anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a light emitting auxiliary layer/a third hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

10 Anode/hole injection layer/first hole transport layer/light emitting auxiliary layer/second hole transport layer/third hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

11 Anode/hole injection layer/first hole transport layer/second hole transport layer/third hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

12 Anode/hole injection layer/first hole transport layer/second hole transport layer/third hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

13 Anode/hole injection layer/first hole transport layer/second hole transport layer/light-emitting auxiliary layer/third hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

14 Anode/hole injection layer/first hole transport layer/light emitting auxiliary layer/second hole transport layer/third hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

15 Anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer;

16 Anode/hole injection layer/first hole transport layer/second hole transport layer/light-emitting auxiliary layer/light-emitting layer/electron transport layer/electron injection layer/cathode/capping layer;

17 Anode/hole injection layer/first hole transport layer/light emitting auxiliary layer/second hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer;

18 Anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

19 Anode/hole injection layer/first hole transport layer/second hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

20 Anode/hole injection layer/first hole transport layer/light emitting auxiliary layer/second hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer;

21 Anode/hole injection layer/first hole transport layer/second hole transport layer/third hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode/capping layer;

22 Anode/hole injection layer/first hole transport layer/second hole transport layer/third hole transport layer/light-emitting auxiliary layer/light-emitting layer/electron transport layer/electron injection layer/cathode/capping layer;

23 Anode/hole injection layer/first hole transport layer/second hole transport layer/light-emitting auxiliary layer/third hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode/cover layer;

24 Anode/hole injection layer/first hole transport layer/light emitting auxiliary layer/second hole transport layer/third hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/cover layer;

25 Anode/hole injection layer/first hole transport layer/second hole transport layer/third hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

26 Anode/hole injection layer/first hole transport layer/second hole transport layer/third hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

27 Anode/hole injection layer/first hole transport layer/second hole transport layer/light-emitting auxiliary layer/third hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

28 Anode/hole injection layer/first hole transport layer/light emitting auxiliary layer/second hole transport layer/third hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer.

The organic layers, the cathode and the anode can be prepared by any one method of vacuum evaporation, ink-jet printing, sputtering, plasma, ion plating, spin coating, dipping, screen printing and the like, and the thickness of each layer is not particularly limited, so that good device performance can be obtained. Each of the organic layers described above is preferably prepared using a method of vacuum evaporation, inkjet printing or spin coating. When the vacuum vapor deposition method is used, if the organic layer has a single-layer structure containing a plurality of substances, the organic layer may be formed by vapor deposition of the plurality of substances at a predetermined mass ratio and a predetermined vapor deposition rate ratio.

The thickness of each organic layer is usually 5nm to 100. Mu.m, preferably 10nm to 200nm. The thickness of the anode and cathode is adjusted according to the desired transparency.

The organic electroluminescent device provided by the invention can be applied to the fields of illumination, display and the like, and can be specifically exemplified by a large-size display such as a smart phone display screen, a tablet personal computer display screen, an intelligent wearable device display screen, a television and the like, VR, an automobile tail lamp and the like.

The technical scheme and technical effects of the present invention will be further described below with examples and comparative examples.

The mass spectrum of the compound of the invention uses a G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer of the Wolts company, england, chloroform as a solvent;

the elemental analysis was carried out using a Vario EL cube organic elemental analyzer from Elementar, germany, and the sample mass was 5 to 10mg.

Synthesis example 1: synthesis of Compounds HT1-3

AA-3 (4.66 g,50 mmol), BB-3 (19.87 g,50 mmol), sodium tert-butoxide (9.61 g,100 mmol) and toluene (250 ml) were added to the reaction flask under nitrogen atmosphere, and the mixture was stirred and then Pd (OAc) was added to the reaction system with continued stirring ₂ (0.11 g,0.5 mmol) and 0.5M P (t-Bu) ₃ Toluene solution (2 ml), the reaction system was heated to reflux, and reacted at reflux for 6 hours. After the completion of the reaction, the mixture was cooled to room temperature, washed with distilled water, extracted with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure, and the obtained residue was recrystallized from toluene/methanol (volume ratio 6:1) to give compound CC-3 (16.79 g, yield 82%). Mass spectrum m/z:409.1849 (theory: 409.1830).

CC-3 (12.29 g,30 mmol), DD-3 (11.92 g,30 mmol), sodium tert-butoxide (5.77 g,60 mmol) and toluene (150 ml) were added to the flask under nitrogen and Pd was added continuously with stirring ₂ (dba) ₃ (0.32 g,0.36 mmol) and 0.5M P (t-Bu) ₃ Toluene solution (1.5 ml), and was heated under reflux for 7 hours. After the completion of the reaction, the mixture was cooled to room temperature, washed with distilled water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, filtered, the filtrate was distilled under reduced pressure, and the obtained residue was recrystallized from toluene/methanol (volume ratio 9:1) to give compound HT1-3 (17.42 g, yield 80%). The purity of the solid detected by HPLC is not less than 99.98%. Mass spectrum m/z:725.3066 (theory: 725.3083). Theoretical element content (%) C ₅₆ H ₃₉ N: c,92.66; h,5.42; n,1.93. Measured element content (%): c,92.68; h,5.45; n,1.90.

Synthesis example 2: synthesis of Compound HT1-30

The AA-3, BB-3 and DD-3 were successively replaced with an equimolar amount of AA-30, BB-30 and DD-30, and the other steps were the same as those of Synthesis example 1, to obtain Compound HT1-30 (18.68 g, yield 78%). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:797.3459 (theory: 797.3478). Theoretical elementContent (%) C ₅₉ H ₄₇ NSi: c,88.79; h,5.94; n,1.76. Measured element content (%): c,88.80; h,5.97; n,1.73.

Synthesis example 3: synthesis of Compound HT1-55

The AA-3, BB-3 and DD-3 were successively replaced with AA-50, DD-30 and DD-30 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-55 (18.05 g, yield 75%). The purity of the solid detected by HPLC is not less than 99.99%. Mass spectrum m/z:801.3375 (theory: 801.3396). Theoretical element content (%) C ₆₂ H ₄₃ N: c,92.85; h,5.40; n,1.75. Measured element content (%): c,92.84; h,5.42; n,1.74.

Synthesis example 4: synthesis of Compound HT1-60

AA-3, BB-3 and DD-3 were successively replaced with AA-55, BB-60 and DD-60 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-60 (17.56 g, yield 73%). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:802.0345 (theory: 802.0330). Theoretical element content (%) C ₆₂ H ₄₃ N: c,92.85; h,5.40; n,1.75. Measured element content (%): c,92.86; h,5.44; n,1.72.

Synthesis example 5: synthesis of Compound HT1-66

The AA-3, BB-3 and DD-3 were successively replaced with AA-66, DD-30 and BB-60 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-66 (17.99 g, yield 74%). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:810.3979 ( Theoretical value: 810.3960). Theoretical element content (%) C ₆₂ H ₃₄ D ₉ N: c,91.81; h,6.46; n,1.73. Measured element content (%): c,91.83; h,6.42; n,1.75.

Synthesis example 6: synthesis of Compound HT1-82

The same procedure as in Synthesis example 3 was followed except for substituting DD-30 with DD-82 in an equimolar amount to give Compound HT1-82 (17.68 g, yield 71%). The purity of the solid detected by HPLC is not less than 99.96%. Mass spectrum m/z:829.3721 (theory: 829.3709). Theoretical element content (%) C ₆₄ H ₄₇ N: c,92.61; h,5.71; n,1.69. Measured element content (%): c,92.66; h,5.68; n,1.68.

Synthesis example 7: synthesis of Compounds HT1-94

The AA-3, BB-3 and DD-3 were successively replaced with AA-94, DD-30 and BB-60 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-94 (16.48 g, yield 69%). The purity of the solid detected by HPLC is not less than 99.92%. Mass spectrum m/z:795.3878 (theory: 795.3865). Theoretical element content (%) C ₆₁ H ₄₉ N: c,92.04; h,6.20; n,1.76. Measured element content (%): c,92.06; h,6.25; n,1.72.

Synthesis example 8: synthesis of Compounds HT1-124

The AA-3, BB-3 and DD-3 were successively replaced with AA-124, DD-30 and DD-124 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-124 (17.75 g, 67% yield). The purity of the solid detected by HPLC is not less than 99.96%. Mass spectrometry m/z:882.4039 (theory: 882.4022). Theoretical element content (%) C ₆₈ H ₄₂ D ₅ N: c,92.48; h,5.93; n,1.59. Measured element content (%): c,92.47; h,5.96; n,1.58.

Synthesis example 9: synthesis of Compound HT1-142

The AA-3, BB-3 and DD-3 were successively replaced with AA-142, BB-142 and DD-30 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-142 (16.74 g, yield 76%). The purity of the solid detected by HPLC is not less than 99.93 percent. Mass spectrum m/z:733.3720 (theory: 733.3709). Theoretical element content (%) C ₅₆ H ₄₇ N: c,91.64; h,6.45; n,1.91. Measured element content (%): c,91.60; h,6.44; n,1.96.

Synthesis example 10: synthesis of Compounds HT1-162

BB-3 and DD-3 were successively replaced with BB-162 and DD-162 in equimolar amounts, and the same procedure as in Synthesis example 1 was repeated to obtain Compound HT1-162 (15.61 g, yield: 77%). The purity of the solid detected by HPLC is not less than 99.94%. Mass spectrum m/z:675.2912 (theory: 675.2926). Theoretical element content (%) C ₅₂ H ₃₇ N: c,92.41; h,5.52; n,2.07. Measured element content (%): c,92.46; h,5.49; n,2.06.

Synthesis example 11: synthesis of Compound HT1-202

The AA-3, BB-3 and DD-3 were successively replaced with AA-55, BB-202 and DD-202 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-202 (16.26 g, yield 74%) ). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:751.3229 (theory: 751.3239). Theoretical element content (%) C ₅₈ H ₄₁ N: c,92.64; h,5.50; n,1.86. Measured element content (%): c,92.66; h,5.51; n,1.85.

Synthesis example 12: synthesis of Compound HT1-207

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The AA-3, BB-3 and DD-3 were successively replaced with AA-55, BB-162 and DD-202 in equimolar amounts, and the other steps were the same as those of Synthesis example 1, to obtain Compound HT1-207 (16.02 g, yield 79%). The purity of the solid detected by HPLC is not less than 99.97%. Mass spectrum m/z:675.2935 (theory: 675.2926). Theoretical element content (%) C ₅₂ H ₃₇ N: c,92.41; h,5.52; n,2.07. Measured element content (%): c,92.40; h,5.57; n,2.05.

Synthesis example 13: synthesis of Compounds HT1-217

The AA-3, BB-3 and DD-3 were successively replaced with AA-55, BB-217 and DD-217 in equimolar amounts, and the other steps were the same as those of Synthesis example 1 to obtain Compound HT1-217 (15.21 g, yield 75%). The purity of the solid detected by HPLC is not less than 99.93 percent. Mass spectrum m/z:675.2908 (theory: 675.2926). Theoretical element content (%) C ₅₂ H ₃₇ N: c,92.41; h,5.52; n,2.07. Measured element content (%): c,92.39; h,5.54; n,2.08.

Synthesis example 14: synthesis of Compounds HT1-241

AA-3, BB-3 and DD-3 were successively replaced with AA-55, BB-241 and DD-241 in equimolar amounts, and the other steps were the same as those of Synthesis example 1, namelyCompound HT1-241 (17.38 g, 71% yield) was obtained. The purity of the solid detected by HPLC is not less than 99.91 percent. Mass spectrum m/z:815.4499 (theory: 815.4491). Theoretical element content (%) C ₆₂ H ₅₇ N: c,91.24; h,7.04; n,1.72. Measured element content (%): c,91.29; h,7.00; n,1.71.

Synthesis example 15: synthesis of Compounds HT1-259

AA-3, BB-3 and DD-3 were successively replaced with an equimolar amount of AA-259, BB-259 and DD-259, and the same procedure as in Synthesis example 1 was repeated to obtain Compound HT1-259 (15.84 g, 67% yield). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:787.4196 (theory: 787.4178). Theoretical element content (%) C ₆₀ H ₅₃ N: c,91.44; h,6.78; n,1.78. Measured element content (%): c,91.40; h,6.80; n,1.79.

Synthesis example 16: synthesis of Compound HT1-278

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The AA-3, BB-3 and DD-3 were successively replaced with AA-278, BB-162 and DD-202 in equimolar amounts, and the other steps were the same as those of Synthesis example 1, to obtain Compound HT1-278 (17.14 g, yield 76%). The purity of the solid detected by HPLC is not less than 99.96%. Mass spectrum m/z:751.3261 (theory: 751.3239). Theoretical element content (%) C ₅₈ H ₄₁ N: c,92.64; h,5.50; n,1.86. Measured element content (%): c,92.63; h,5.52; n,1.86.

Synthesis example 17: synthesis of Compound HT2-9

AA-30 (18.34 g,55.00 mmol) and BB-30 were added to the flask under nitrogen protection(12.61 g,55.00 mmol), sodium t-butoxide (10.57 g,110.00 mmol) and toluene (275 ml) were mixed with stirring, and Pd (OAc) was added to the reaction system with continued stirring ₂ (0.12 g,0.55 mmol) and 0.5M P (t-Bu) ₃ Toluene solution (2.20 ml), the reaction system was heated to reflux, and the reaction was refluxed for 6.5h. After the completion of the reaction, the mixture was cooled to room temperature, washed with distilled water, extracted with dichloromethane, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure, and the obtained residue was recrystallized from toluene/methanol (volume ratio 6:1) to give compound CC-30 (21.46 g, yield 81%). Mass spectrum m/z:481.2215 (theory: 481.2226).

Under the protection of nitrogen, dd-9 (8.65 g,35.00 mmol), CC-30 (16.86 g,35.00 mmol), sodium tert-butoxide (6.73 g,70.00 mmol) and toluene (175 ml) are added into a reaction flask in sequence, stirred and mixed, pd is added into the reaction system by continuous stirring ₂ (dba) ₃ (0.32 g,0.35 mmol) and BINAP (0.65 g,1.05 mmol) were dissolved by stirring, and reacted under reflux under the protection of nitrogen for 8 hours, after the completion of the reaction, methylene chloride and distilled water were added to the reaction solution and stirred, and liquid-separated extraction was performed. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, and the resulting residue was recrystallized from toluene/methanol (volume ratio 7:1) to finally give compound HT2-9 (17.91 g, yield 79%). The purity of the solid detected by HPLC is not less than 99.96%. Mass spectrum m/z:647.2653 (theory: 647.2644). Theoretical element content (%) C ₄₆ H ₃₇ NOSi: c,85.28; h,5.76; n,2.16. Measured element content (%): c,85.26; h,5.79; n,2.13.

Synthesis example 18: synthesis of Compound HT2-22

The AA-30 and BB-30 were successively replaced with an equimolar amount of AA-55 and DD-30, and the other steps were the same as those in Synthesis example 17 to obtain Compound HT2-22 (18.25 g, yield 80%). The purity of the solid detected by HPLC is not less than 99.98%. Mass spectrum m/z:651.2550 (theory: 651.2562). Theoretical element content (%) C ₄₉ H ₃₃ NO：C90.29; h,5.10; n,2.15. Measured element content (%): c,90.31; h,5.07; n,2.18.

Synthesis example 19: synthesis of Compound HT2-29

AA-30, BB-30, DD-9 were successively replaced with AA-29, DD-30, DD-29 in equimolar amounts, and the other steps were the same as in Synthesis example 17, to give Compound HT2-29 (17.57 g, yield 77%). The purity of the solid detected by HPLC is not less than 99.96%. Mass spectrum m/z:651.2550 (theory: 651.2562). Theoretical element content (%) C ₄₉ H ₃₃ NO: c,90.29; h,5.10; n,2.15. Measured element content (%): c,90.31; h,5.08; n,2.17.

Synthesis example 20: synthesis of Compound HT2-39

The AA-30, BB-30 and dd-9 were successively replaced with equal molar amounts of AA-259, BB-60 and dd-29, and the same procedure as in Synthesis example 17 was repeated, to obtain Compound HT2-39 (17.79 g, yield 78%). The purity of the solid detected by HPLC is not less than 99.97%. Mass spectrum m/z:651.2551 (theory: 651.2562). Theoretical element content (%) C ₄₉ H ₃₃ NO: c,90.29; h,5.10; n,2.15. Measured element content (%): c,90.31; h,5.09; n,2.16.

Synthesis example 21: synthesis of Compound HT2-96

The AA-30, BB-30 and dd-9 were successively replaced with equal molar amounts of AA-55, BB-96 and dd-96, and the same procedure was followed as in Synthesis example 17 to obtain Compound HT2-96 (19.36 g, yield 76%). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:727.2866 (theory: 727.2875). Theoretical elementElement content (%) C ₅₅ H ₃₇ NO: c,90.75; h,5.12; n,1.92. Measured element content (%): c,90.77; h,5.09; n,1.95.

Synthesis example 22: synthesis of Compound HT2-106

The AA-30 and BB-30 were successively replaced with an equimolar amount of AA-124 and BB-60, and the same procedure as in Synthesis example 17 was repeated to obtain Compound HT2-106 (17.24 g, yield: 75%). The purity of the solid detected by HPLC is not less than 99.96%. Mass spectrum m/z:656.2891 (theory: 656.2876). Theoretical element content (%) C ₄₉ H ₂₈ D ₅ NO: c,89.60; h,5.83; n,2.13. Measured element content (%): c,89.58; h,5.84; n,2.16.

Synthesis example 23: synthesis of Compound HT2-116

The AA-30, BB-30 and DD-9 were successively replaced with AA-55, DD-30 and DD-116 in equimolar amounts, and the other steps were the same as those of Synthesis example 17, whereby Compound HT2-116 (17.83 g, yield 70%) was obtained. The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:727.2865 (theory: 727.2875). Theoretical element content (%) C ₅₅ H ₃₇ NO: c,90.75; h,5.12; n,1.92. Measured element content (%): c,90.77; h,5.15; n,1.89.

Synthesis example 24: synthesis of Compound HT2-127

The AA-30, BB-30 and DD-9 were successively replaced with AA-55, DD-30 and DD-127 in equimolar amounts, and the other steps were the same as those of Synthesis example 17, to obtain Compound HT2-127 (18.42 g, yield 75%). The purity of the solid detected by HPLC is not less than 99.93 percent.Mass spectrum m/z:701.2711 (theory: 701.2719). Theoretical element content (%) C ₅₃ H ₃₅ NO: c,90.70; h,5.03; n,2.00. Measured element content (%): c,90.69; h,5.04; n,2.03.

Synthesis example 25: synthesis of Compound HT2-155

The AA-30, BB-30 and DD-9 were successively replaced with equal molar amounts of AA-55, DD-202 and DD-96, and the other steps were the same as those of Synthesis example 17, to obtain Compound HT2-155 (18.19 g, yield 80%). The purity of the solid detected by HPLC is not less than 99.97%. Mass spectrum m/z:649.2419 (theory: 649.2406). Theoretical element content (%) C ₄₉ H ₃₁ NO: c,90.57; h,4.81; n,2.16. Measured element content (%): c,90.54; h,4.79; n,2.18.

Synthesis example 26: synthesis of Compound HT2-196

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The AA-30 and BB-30 were successively replaced with an equimolar amount of AA-55 and DD-259, and the same procedure as in Synthesis example 17 was repeated to obtain Compound HT2-196 (18.14 g, yield 68%). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:761.3643 (theory: 761.3658). Theoretical element content (%) C ₅₇ H ₄₇ NO: c,89.85; h,6.22; n,1.84. Measured element content (%): c,89.82; h,6.23; n,1.81.

Synthesis example 27: synthesis of Compound HT2-214

The AA-30 and BB-30 were successively replaced with an equimolar amount of AA-66 and DD-202, and the other steps were the same as those of Synthesis example 17 to obtain Compound HT2-214 (17.29 g, yield 75%). HPLC detectionThe purity of the solid is not less than 99.94 percent. Mass spectrum m/z:658.2988 (theory: 658.2971). Theoretical element content (%) C ₄₉ H ₂₂ D ₉ NO: c,89.33; h,6.12; n,2.13. Measured element content (%): c,89.31; h,6.14; n,2.16.

Synthesis example 28: synthesis of Compound HT2-220

The AA-30 and BB-30 were successively replaced with an equimolar amount of AA-55 and BB-220, and the same procedure was followed as in Synthesis example 17 to obtain Compound HT2-220 (18.55 g, 73% yield). The purity of the solid detected by HPLC is not less than 99.95%. Mass spectrum m/z:725.2701 (theory: 725.2719). Theoretical element content (%) C ₅₅ H ₃₅ NO: c,91.01; h,4.86; n,1.93. Measured element content (%): c,91.02; h,4.83; n,1.95.

Synthesis example 29: synthesis of Compound HT2-251

AA-30, BB-30, dd-9 were successively replaced with AA-251, BB-162, dd-96 in equimolar amounts, and the other steps were the same as in Synthesis example 17, to give Compound HT2-251 (14.56 g, yield 68%). The purity of the solid detected by HPLC is not less than 99.94%. Mass spectrum m/z:611.3179 (theory: 611.3188). Theoretical element content (%) C ₄₅ H ₄₁ NO: c,88.34; h,6.75; n,2.29. Measured element content (%): c,88.36; h,6.72; n,2.31.

Synthesis example 30: synthesis of Compound HT2-273

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AA-30, BB-30, DD-9 were replaced with equimolar amounts of AA-3, DD-273, and the other steps were the same as in Synthesis example 17, to giveTo compound HT2-273 (15.33 g, 74% yield). The purity of the solid detected by HPLC is not less than 99.92%. Mass spectrum m/z:591.2039 (theory: 591.2021). Theoretical element content (%) C ₄₃ H ₂₉ NS: c,87.28; h,4.94; n,2.37. Measured element content (%): c,87.31; h,4.92; n,2.34.

Synthesis example 31: synthesis of Compounds HT2-287

The AA-30, BB-30 and dd-9 were successively replaced with equal molar amounts of AA-55, BB-3 and dd-273, and the same procedure was followed as in Synthesis example 17 to obtain Compound HT2-287 (18.70 g, yield 80%). The purity of the solid detected by HPLC is not less than 99.97%. Mass spectrum m/z:667.2311 (theory: 667.2334). Theoretical element content (%) C ₄₉ H ₃₃ NS: c,88.12; h,4.98; n,2.10. Measured element content (%): c,88.15; h,4.96; n,2.13.

Synthesis example 32: synthesis of Compound HT2-310

AA-30, BB-30, DD-9 were successively replaced with AA-310, DD-30, DD-273 in equimolar amounts, and the other steps were the same as in Synthesis example 17, to give Compound HT2-310 (19.26 g, yield 76%). The purity of the solid detected by HPLC is not less than 99.92%. Mass spectrum m/z:723.2977 (theory: 723.2960). Theoretical element content (%) C ₅₃ H ₄₁ NS: c,87.93; h,5.71; n,1.93. Measured element content (%): c,87.95; h,5.69; n,1.90.

Synthesis example 33: synthesis of Compound HT2-315

The AA-30, BB-30 and DD-9 are replaced by AA-55, DD-82 and DD-2 with equimolar amounts in sequence73, other steps were carried out in the same manner as in Synthesis example 17, so as to obtain Compound HT2-315 (17.29 g, yield 71%). The purity of the solid detected by HPLC is not less than 99.93 percent. Mass spectrum m/z:695.2631 (theory: 695.2647). Theoretical element content (%) C ₅₁ H ₃₇ NS: c,88.02; h,5.36; n,2.01. Measured element content (%): c,88.04; h,5.33; n,2.02.

Synthesis example 34: synthesis of Compound HT2-341

The AA-30, BB-30 and DD-9 were successively replaced with equal molar amounts of AA-3, DD-124 and DD-341, and the same procedure was followed as in Synthesis example 17 to obtain Compound HT2-341 (19.53 g, yield 75%). The purity of the solid detected by HPLC is not less than 99.94%. Mass spectrum m/z:743.2630 (theory: 743.2647). Theoretical element content (%) C ₅₅ H ₃₇ NS: c,88.79; h,5.01; n,1.88. Measured element content (%): c,88.81; h,5.03; n,1.86.

Synthesis example 35: synthesis of Compound HT2-363

The AA-30, BB-30 and DD-9 were successively replaced with equal molar amounts of AA-55, DD-202 and DD-363, and the other steps were the same as those of Synthesis example 17 to obtain Compound HT2-363 (17.23 g, yield 74%). The purity of the solid detected by HPLC is not less than 99.96%. Mass spectrum m/z:665.2193 (theory: 665.2177). Theoretical element content (%) C ₄₉ H ₃₁ NS: c,88.39; h,4.69; n,2.10. Measured element content (%): c,88.41; h,4.67; n,2.12.

The following are other compounds used in the device preparation examples in addition to the compounds of formula (I) and formula (II) described in the present invention:

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the organic materials in the device preparation examples are purified by sublimation, and the purity is over 99.99 percent. The ITO glass substrate and the ITO/Ag/ITO glass substrate used in the device preparation example are all purchased in the market.

Test software, a computer, a K2400 digital source meter from Keithley company, U.S. and a PR788 spectral scanning luminance meter from Photo Research, U.S. are combined into a combined IVL test system, and the device prepared by the invention is tested at atmospheric pressure and room temperature at a current density of 15mA/cm ² Light-emitting efficiency and driving voltage at the time. The lifetime of the devices prepared according to the invention (decay of brightness to 95% of the initial brightness) was tested using the Mcscience M6000 OLED lifetime test system at atmospheric pressure and room temperature. The test results are shown in tables 1 to 4.

Comparative device preparation example 1: contrast device 1

Firstly, an ITO glass substrate is ultrasonically cleaned by deionized water for 2 times each for 20 minutes, then sequentially ultrasonically cleaned by isopropanol, acetone and methanol for 20 minutes respectively, then exposed to ultraviolet rays and ozone for 30 minutes, and finally placed in a vacuum evaporation device for standby.

The following layers are evaporated layer by layer on the ITO glass substrate: a. 2-TNATA is used as a hole injection layer with the thickness of 40nm; b. HT1-30 is used as a first hole transport layer, and the thickness is 60nm; c. RH-1, RH-2 and Ir (dpm) PQ ₂ (mass ratio of 64:32:4) as a light-emitting layer, the thickness was 35nm; d. BAlq is used as a hole blocking layer with the thickness of 25nm; e. NBphen and Liq (mass ratio 7:3) as electron transport layers with thickness of 25nm; f. LiF is used as an electron injection layer, and the thickness is 1nm; g. al was used as a cathode and the thickness was 100nm.

Comparative device preparation examples 2 to 7: contrast devices 2 to 7

The HT1-30 in the first hole transport layer was replaced with HT1-55, HT1-207, HT1-259, HT2-29, HT2-106, HT2-363, respectively, and the other steps were the same as those of comparative device preparation 1, thereby obtaining comparative devices 2-7.

Device preparation example 1: device 1

The following layers are evaporated layer by layer on the ITO glass substrate: a. 2-TNATA is used as a hole injection layer with the thickness of 40nm; b. HT1-30 is used as a first hole transport layer, and the thickness is 30nm; c. HT2-29 as a second hole transport layer, having a thickness of 30nm; d. RH-1, RH-2 and Ir (dpm) PQ ₂ (mass ratio of 64:32:4) as a light-emitting layer, the thickness was 35nm; e. BAlq is used as a hole blocking layer with the thickness of 25nm; f. NBphen and Liq (mass ratio 7:3) as electron transport layers with thickness of 25nm; g. LiF is used as an electron injection layer, and the thickness is 1nm; h. al was used as a cathode and the thickness was 100nm.

Device preparation example 2: device 2

The device 2 was obtained by replacing HT2-29 in the second hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 1.

Device preparation example 3: device 3

The device 3 was obtained by replacing HT1-30 in the first hole transport layer with HT1-55, replacing HT2-29 in the second hole transport layer with HT2-39, and performing the same procedure as in device manufacturing example 1.

Device preparation example 4: device 4

The device 4 was obtained by replacing HT1-30 in the first hole transport layer with HT1-55, replacing HT2-29 in the second hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 1.

Device preparation example 5: device 5

The device 5 was obtained by replacing HT1-30 in the first hole transport layer with HT1-55, replacing HT2-29 in the second hole transport layer with HT2-273, and performing the same procedures as those of device manufacturing example 1.

Device preparation example 6: device 6

The device 6 was obtained by replacing HT1-30 in the first hole transport layer with HT1-82, replacing HT2-29 in the second hole transport layer with HT2-96, and performing the same procedure as in device manufacturing example 1.

Device preparation example 7: device 7

Device 7 was obtained by replacing HT1-30 in the first hole transport layer with HT1-124, and performing the same procedure as in device manufacturing example 1.

Device preparation example 8: device 8

The device 8 was obtained by replacing HT1-30 in the first hole transport layer with HT1-124, replacing HT2-29 in the second hole transport layer with HT2-363, and performing the same procedure as in device manufacturing example 1.

Device preparation example 9: device 9

The device 9 was obtained by replacing HT1-30 in the first hole transport layer with HT1-142, replacing HT2-29 in the second hole transport layer with HT2-341, and performing the same procedures as those of device manufacturing example 1.

Device preparation example 10: device 10

The device 10 was obtained by replacing HT1-30 in the first hole transport layer with HT1-162, replacing HT2-29 in the second hole transport layer with HT2-363, and performing the same procedure as in device manufacturing example 1.

Device preparation example 11: device 11

The device 11 was obtained by replacing HT1-30 in the first hole transport layer with HT1-207, replacing HT2-29 in the second hole transport layer with HT2-39, and performing the same procedure as in device manufacturing example 1.

Device preparation example 12: device 12

The device 12 was obtained by replacing HT1-30 in the first hole transport layer with HT1-207, replacing HT2-29 in the second hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 1.

Device preparation example 13: device 13

The device 13 was obtained by replacing HT1-30 in the first hole transport layer with HT1-207, replacing HT2-29 in the second hole transport layer with HT2-273, and performing the same procedures as those of device manufacturing example 1.

Device preparation example 14: device 14

The device 14 was obtained by replacing HT1-30 in the first hole transport layer with HT1-259 and performing the same procedure as in device manufacturing example 1.

Device preparation example 15: device 15

The device 15 was obtained by replacing HT1-30 in the first hole transport layer with HT1-259 and replacing HT2-29 in the second hole transport layer with HT2-106, and the other steps were the same as those of device manufacturing example 1.

TABLE 1

Comparative device preparation example 8: contrast device 8

The following layers are evaporated layer by layer on the ITO glass substrate: a. p-1 and HT1-60 (mass ratio 7:100) as hole injection layers, thickness 30nm; b. HT1-60 is used as a first hole transport layer, and the thickness is 70nm; c. GH-1, GH-2 and Ir (ppy) ₂ (m-bppy) (mass ratio 47:47:6) as a light-emitting layer, with a thickness of 35nm; d. BAlq is used as a hole blocking layer with the thickness of 25nm; e. NBphen and Liq (mass ratio 7:3) as electron transport layers with thickness of 25nm; f. LiF is used as an electron injection layer, and the thickness is 1nm; g. al was used as a cathode and the thickness was 100nm.

Comparative device preparation examples 9 to 13: contrast devices 9 to 13

The hole injection layer and HT1-60 in the first hole transport layer were replaced with HT1-66, HT1-217, HT2-9, HT2-22, HT2-214, respectively, and the other steps were the same as those of comparative device preparation 8, thereby obtaining comparative devices 9-13.

Device preparation example 16: device 16

The following layers are evaporated layer by layer on the ITO glass substrate: a. p-1 and HT2-9 (mass ratio 7:100) as hole injection layers, thickness 30nm; b. HT2-9 as a first hole transport layer, having a thickness of 35nm; c. HT1-3 as a second hole transport layer, having a thickness of 35nm; d. GH-1, GH-2 and Ir (ppy) ₂ (m-bppy) (mass ratio 47:47:6) as a light-emitting layer, with a thickness of 35nm; e. BAlq is used as a hole blocking layer with the thickness of 25nm; f. NBphen and Liq (mass ratio 7:3) as electron transport layers with thickness of 25nm; g. LiF is used as an electron injection layer, and the thickness is 1nm; h. al was used as a cathode and the thickness was 100nm.

Device preparation example 17: device 17

The device 17 was obtained by replacing HT1-3 in the second hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 16.

Device preparation example 18: device 18

The device 18 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-251, replacing HT1-3 in the second hole transport layer with HT1-217, and performing the same procedure as in device manufacturing example 16.

Device preparation example 19: device 19

The device 19 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-315, replacing HT1-3 in the second hole transport layer with HT1-60, and performing the same procedure as in device manufacturing example 16.

Device preparation example 20: device 20

The device 20 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-22, replacing HT1-3 in the second hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 16.

Device preparation example 21: device 21

The device 21 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-116, and performing the same procedure as in device manufacturing example 16.

Device preparation example 22: device 22

The device 22 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-127, replacing HT1-3 in the second hole transport layer with HT1-94, and performing the same procedure as in device manufacturing example 16.

Device preparation example 23: device 23

The device 23 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-155, replacing HT1-3 in the second hole transport layer with HT1-60, and performing the same procedure as in device manufacturing example 16.

Device preparation example 24: device 24

The device 24 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-196, replacing HT1-3 in the second hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 16.

Device preparation example 25: device 25

The device 25 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-196, replacing HT1-3 in the second hole transport layer with HT1-217, and performing the same procedure as in device manufacturing example 16.

Device preparation example 26: device 26

Device 26 was obtained by substituting HT2-9 in the hole injection layer and the first hole transport layer with HT2-214, and performing the same procedures as in device manufacturing example 16.

Device preparation example 27: device 27

The device 27 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-214, replacing HT1-3 in the second hole transport layer with HT1-60, and performing the same procedure as in device manufacturing example 16.

Device preparation example 28: device 28

The device 28 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-214, replacing HT1-3 in the second hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 16.

Device preparation example 29: device 29

The device 29 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-220, replacing HT1-3 in the second hole transport layer with HT1-217, and performing the same procedure as in device manufacturing example 16.

Device preparation example 30: device 30

The device 30 was obtained by replacing HT2-9 in the hole injection layer and the first hole transport layer with HT2-287, replacing HT1-3 in the second hole transport layer with HT1-241, and performing the same steps as those of device manufacturing example 16.

TABLE 2

Comparative device preparation example 14: contrast device 14

Firstly, the ITO/Ag/ITO glass substrate is ultrasonically cleaned by deionized water for 2 times, each time for 20 minutes, then sequentially ultrasonically cleaned by isopropanol, acetone and methanol for 20 minutes respectively, then exposed to ultraviolet rays and ozone for 30 minutes, and finally placed in a vacuum evaporation device for standby.

The following layers are evaporated layer by layer on the ITO/Ag/ITO glass substrate: a. hat is used as a hole injection layer, and the thickness is 15nm; b. HT-1 as a first hole transport layer, having a thickness of 35nm; c. HT1-66 as a second hole transport layer, thickness of 60nm; d. BANE and BD (mass ratio 95:5) as light emitting layers with a thickness of 35nm; e. TPBi is used as a hole blocking layer, and the thickness is 25nm; f. NBphen and Liq (mass ratio 7:3) as electron transport layers with thickness of 25nm; g. LiF is used as an electron injection layer, and the thickness is 0.1nm; h. mg and Ag (mass ratio 1:1) are used as cathodes with the thickness of 10nm; i: CP-4 was used as a coating layer with a thickness of 100nm.

Comparative device preparation examples 15 to 17: contrast devices 15-17

The comparative devices 15 to 17 were obtained by replacing HT1-66 in the second hole transport layer with HT1-259, HT2-39, and HT2-106, respectively, and performing the same procedure as in comparative device preparation example 14.

Device preparation example 31: device 31

The following layers are evaporated layer by layer on the ITO/Ag/ITO glass substrate: a. hat is used as a hole injection layer, and the thickness is 15nm; b. HT-1 as a first hole transport layer, having a thickness of 35nm; c. HT1-3 as a second hole transport layer, having a thickness of 30nm; d. HT2-39 as a third hole transport layer, having a thickness of 30nm; e. BANE and BD (mass ratio 95:5) as light emitting layers with a thickness of 35nm; f. TPBi is used as a hole blocking layer, and the thickness is 25nm; g. NBphen and Liq (mass ratio 7:3) as electron transport layers with thickness of 25nm; h. LiF is used as an electron injection layer, and the thickness is 0.1nm; i. mg and Ag (mass ratio 1:1) are used as cathodes with the thickness of 10nm; j: CP-4 was used as a coating layer with a thickness of 100nm.

Device preparation example 32: device 32

The device 32 was obtained by replacing HT2-39 in the third hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 31.

Device preparation example 33: device 33

The device 33 was obtained by replacing HT2-39 in the third hole transport layer with HT2-363, and performing the same procedures as in device manufacturing example 31.

Device preparation example 34: device 34

The device 34 was obtained by replacing HT1-3 in the second hole transport layer with HT1-60, and performing the same procedure as in device manufacturing example 31.

Device preparation example 35: device 35

The device 35 was obtained by replacing HT1-3 in the second hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 31.

Device preparation example 36: device 36

The device 36 was obtained by replacing HT1-3 in the second hole transport layer with HT1-66, replacing HT2-39 in the third hole transport layer with HT2-273, and performing the same procedures as those performed in device manufacturing example 31.

Device preparation example 37: device 37

The device 37 was obtained by replacing HT1-3 in the second hole transport layer with HT1-202, replacing HT2-39 in the third hole transport layer with HT2-29, and performing the same procedure as in device manufacturing example 31.

Device preparation example 38: device 38

Device 38 was obtained by replacing HT1-3 in the second hole transport layer with HT1-241, replacing HT2-39 in the third hole transport layer with HT2-196, and performing the same procedure as in device manufacturing example 31.

Device preparation example 39: device 39

The device 39 was obtained by replacing HT1-3 in the second hole transport layer with HT1-259 and replacing HT2-39 in the third hole transport layer with HT2-29, and the other steps were the same as those in device manufacturing example 31.

Device preparation example 40: device 40

The device 40 was obtained by replacing HT1-3 in the second hole transport layer with HT1-259, replacing HT2-39 in the third hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 31.

TABLE 3 Table 3

Light emitting device	A second hole transport layer	Third hole transport layer	Driving voltage (V)	Luminous efficiency (cd/A)	Lifetime (h)
						Contrast device 14	HT1-66	——	4.7	9.97	104.8
Contrast device 15	HT1-259	——	4.9	10.11	98.5
						Contrast device 16	HT2-39	——	4.8	9.69	99.5
Contrast device 17	HT2-106	——	4.6	10.35	102.6
						Device 31	HT1-3	HT2-39	4.1	14.48	143.4
Device 32	HT1-3	HT2-106	3.9	14.81	146.4
						Device 33	HT1-3	HT2-363	4.1	14.36	142.2
Device 34	HT1-60	HT2-39	4.1	14.55	144.2
						Device 35	HT1-66	HT2-39	3.9	15.21	148.5
Device 36	HT1-66	HT2-273	4.0	14.69	145.7
						Device 37	HT1-202	HT2-29	4.2	13.76	140.5
Device 38	HT1-241	HT2-196	4.3	13.94	139.7
						Device 39	HT1-259	HT2-29	4.2	14.12	141.3
Device 40	HT1-259	HT2-106	4.0	14.97	147.1

Comparative device preparation example 18: contrast device 18

The following layers are evaporated layer by layer on the ITO/Ag/ITO glass substrate: a. 2-TNATA is used as a hole injection layer with the thickness of 60nm; b. HT-6 is used as a first hole transport layer, and the thickness of the HT-6 is 30nm; c. HT1-66 as a second hole transport layer, having a thickness of 50nm; d. GH-1, GH-2 and Ir (ppy) ₂ (m-bppy) (mass ratio 48:48:4) as a light-emitting layer, thickness was 35nm; e. TPBi is used as a hole blocking layer, and the thickness is 25nm; f. NBphen and Liq (mass ratio 3:2) are used as electron transport layers with the thickness of 25nm; g. LiF is used as an electron injection layer, and the thickness is 0.1nm; h. mg and Ag (mass ratio 3:7) are used as cathodes with the thickness of 10nm; i: CP-4 was used as a coating layer with a thickness of 100nm.

Comparative device preparation examples 19 to 23: contrast devices 19-23

The comparative devices 19 to 23 were obtained by replacing HT1-66 in the second hole transport layer with HT1-217, HT2-9, HT2-22, HT2-29, and HT2-106, respectively, and performing the same procedure as in comparative device preparation 18.

Device preparation example 41: device 41

The following layers are evaporated layer by layer on the ITO/Ag/ITO glass substrate: a. 2-TNATA is used as a hole injection layer with the thickness of 60nm; b. HT-6 is used as a first hole transport layer, and the thickness of the HT-6 is 30nm; c. HT2-9 as a second hole transport layer, having a thickness of 25nm; d. HT1-60, thickness 25nm; e. GH-1, GH-2 and Ir (ppy) ₂ (m-bppy) (mass ratio 48:48:4) as a light-emitting layer, thickness was 35nm; f. TPBi is used as a hole blocking layer, and the thickness is 25nm; g. NBphen and Liq (mass ratio 3:2) are used as electron transport layers with the thickness of 25nm; h. LiF is used as an electron injection layer, and the thickness is 0.1nm; i. mg and Ag (mass ratio 3:7) are used as cathodes with the thickness of 10nm; j: CP-4 was used as a coating layer with a thickness of 100nm.

Device preparation example 42: device 42

The device 42 was obtained by replacing HT1-60 in the third hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 41.

Device preparation example 43: device 43

The device 43 was obtained by replacing HT2-9 in the second hole transport layer with HT2-22, replacing HT1-60 in the third hole transport layer with HT1-3, and performing the same procedure as in device manufacturing example 41.

Device preparation example 44: device 44

The device 44 was obtained by replacing HT2-9 in the second hole transport layer with HT2-22, replacing HT1-60 in the third hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 41.

Device preparation example 45: device 45

The device 45 was obtained by replacing HT2-9 in the second hole transport layer with HT2-22, replacing HT1-60 in the third hole transport layer with HT1-217, and performing the same procedure as in device manufacturing example 41.

Device preparation example 46: device 46

The device 46 was obtained by replacing HT2-9 in the second hole transport layer with HT2-29, replacing HT1-60 in the third hole transport layer with HT1-94, and performing the same procedure as in device manufacturing example 41.

Device preparation example 47: device 47

Device 47 was obtained by replacing HT2-9 in the second hole transport layer with HT2-39, and performing the same procedures as in device manufacturing example 41.

Device preparation example 48: device 48

The device 48 was obtained by replacing HT2-9 in the second hole transport layer with HT2-39, replacing HT1-60 in the third hole transport layer with HT1-217, and performing the same procedure as in device manufacturing example 41.

Device preparation example 49: device 49

Device 49 was obtained by replacing HT2-9 in the second hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 41.

Device preparation example 50: device 50

The device 50 was obtained by replacing HT2-9 in the second hole transport layer with HT2-106, replacing HT1-60 in the third hole transport layer with HT1-94, and performing the same procedure as in device manufacturing example 41.

Device preparation example 51: device 51

The device 51 was obtained by replacing HT2-9 in the second hole transport layer with HT2-310, replacing HT1-60 in the third hole transport layer with HT1-3, and performing the same procedure as in device manufacturing example 41.

Device preparation example 52: device 52

The device 52 was obtained by replacing HT2-9 in the second hole transport layer with HT2-310, replacing HT1-60 in the third hole transport layer with HT1-66, and performing the same procedure as in device manufacturing example 41.

Device preparation example 53: device 53

The device 53 was obtained by replacing HT2-9 in the second hole transport layer with HT2-363, and performing the same procedure as in device manufacturing example 41.

Device preparation example 54: device 54

The device 54 was obtained by replacing HT2-9 in the second hole transport layer with HT2-363, replacing HT1-60 in the third hole transport layer with HT1-66, and performing the same steps as those of device manufacturing example 41.

Device preparation example 55: device 55

The device 55 was obtained by replacing HT2-9 in the second hole transport layer with HT2-363, replacing HT1-60 in the third hole transport layer with HT1-217, and performing the same steps as those of device manufacturing example 41.

TABLE 4 Table 4

Comparative device preparation example 24: contrast device 24

The following layers are evaporated layer by layer on the ITO/Ag/ITO glass substrate: a. p-1 and HT1-30 (mass ratio 3:100) as hole injection layers, thickness 35nm; b. HT1-30 is used as a first hole transport layer, and the thickness is 75nm; c. RH-1, RH-2 and Ir (dpm) PQ ₂ (mass ratio of 47:47:6) as a light-emitting layer, the thickness was 35nm; d. TPBi is used as a hole blocking layer, and the thickness is 25nm; e. NBphen and Liq (mass ratio 7:3) as electron transport layers with thickness of 25nm; f. LiF is used as an electron injection layer, and the thickness is 0.1nm; g. mg and Ag (mass ratio 1:9) are used as cathodes with the thickness of 10nm; h: CP-4 was used as a coating layer with a thickness of 100nm.

Comparative device preparation examples 25 to 30: contrast devices 25-30

The hole injection layer and HT1-30 in the first hole transport layer were replaced with HT1-55, HT1-66, HT1-259, HT2-29, HT2-39, HT2-106, respectively, and the other steps were the same as those of comparative device preparation 24, thereby obtaining comparative devices 25-30.

Device preparation example 56: contrast device 56

The following layers are evaporated layer by layer on the ITO/Ag/ITO glass substrate: a. p-1 and HT1-30 (mass ratio 3:100) as hole injection layers, thickness 35nm; b. HT1-30 is used as a first hole transport layer, and the thickness is 35nm; c. HT1-66 as a second hole transport layer, having a thickness of 20nm; d. HT2-39 as a third hole transport layer, having a thickness of 20nm; e. RH-1, RH-2 and Ir (dpm) PQ ₂ (mass ratio of 47:47:6) as a light-emitting layer, the thickness was 35nm; f. TPBi is used as a hole blocking layer, and the thickness is 25nm; g. NBphen and Liq (mass ratio 7:3) as electron transport layersThe thickness is 25nm; h. LiF is used as an electron injection layer, and the thickness is 0.1nm; i. mg and Ag (mass ratio 1:9) are used as cathodes with the thickness of 10nm; j: CP-4 was used as a coating layer with a thickness of 100nm.

Device preparation example 57: device 57

The device 57 was obtained by replacing HT1-66 in the second hole transport layer with HT1-259, replacing HT2-39 in the third hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 56.

Device preparation example 58: device 58

The device 58 was obtained by replacing HT2-39 in the third hole transport layer with HT2-363 and performing the same procedure as in device manufacturing example 56.

Device preparation example 59: device 59

The device 59 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-55, replacing HT1-66 in the second hole transport layer with HT1-3, and performing the same procedure as in device manufacturing example 56.

Device preparation example 60: device 60

The device 60 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-55, replacing HT2-39 in the third hole transport layer with HT2-273, and performing the same procedures as those performed in device manufacturing example 56.

Device preparation 61: device 61

The device 61 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-55, replacing HT1-66 in the second hole transport layer with HT1-202, replacing HT2-39 in the third hole transport layer with HT2-29, and performing the same procedure as in device manufacturing example 56.

Device preparation example 62: device 62

The device 62 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-124, replacing HT1-66 in the second hole transport layer with HT1-241, replacing HT2-39 in the third hole transport layer with HT2-273, and performing the same steps as those of device manufacturing example 56.

Device preparation example 63: device 63

The device 63 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-259, replacing HT1-66 in the second hole transport layer with HT1-3, replacing HT2-39 in the third hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 56.

Device preparation example 64: device 64

The device 64 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-259, replacing HT2-39 in the third hole transport layer with HT2-363, and performing the same procedure as in device manufacturing example 56.

Device preparation example 65: device 65

The device 65 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-259 and performing the same procedure as in device manufacturing example 56.

Device preparation example 66: device 66

The device 66 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-278, replacing HT1-66 in the second hole transport layer with HT1-3, replacing HT2-39 in the third hole transport layer with HT2-29, and performing the same procedure as in device manufacturing example 56.

Device preparation 67: device 67

The device 67 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-278 and performing the same procedure as in device manufacturing example 56.

Device preparation example 68: device 68

The device 68 was obtained by replacing HT1-30 in the hole injection layer and the first hole transport layer with HT1-278, replacing HT1-66 in the second hole transport layer with HT1-259, replacing HT2-39 in the third hole transport layer with HT2-106, and performing the same procedure as in device manufacturing example 56.

TABLE 5

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The device data in tables 1 to 5 show that the organic electroluminescent device of the present invention has excellent driving voltage, luminous efficiency and life performance by using the hole transport region of a specific structure.

It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.

Claims

1. An organic electroluminescent device comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode, the organic layer comprises a hole transmission area, a luminescent layer and an electron transmission area, and the hole transmission area comprises at least two hole transmission layers, and the organic electroluminescent device is characterized in that one hole transmission layer contains one of compounds shown as a formula (I), and the other hole transmission layer contains one of compounds shown as a formula (II):

In formula (II), the Ar ₁₀₁ One selected from the following structures:

said R is ₁₀₃ At each time of occurrence of this, the process is completed, is identically or differently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group,One of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, and a group formed by fusing a substituted or unsubstituted C6-C30 aromatic ring to a C3-C7 alicyclic ring, two adjacent R ₁₀₃ Can be linked to form one of a substituted or unsubstituted C3-C7 aliphatic ring and a substituted or unsubstituted C6-C10 aromatic ring;

ar as described ₁₀₂ One selected from the following structures:

wherein X is selected from oxygen atom or sulfur atom;

2. The organic electroluminescent device of claim 1, wherein Ar ₃ One selected from the following structures:

3. The organic electroluminescent device of claim 1, wherein L is ₁ ～L ₃ Independently selected from a single bond or one of the structures shown below:

wherein,the a ₆ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; said b ₆ Each occurrence is identically or differently selected from 0, 1, 2 or 3; the said c ₆ Each occurrence is identically or differently selected from 0, 1 or 2; d is as follows ₆ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5 or 6; said e ₆ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

4. The organic electroluminescent device of claim 1, wherein Ar ₁₀₃ One selected from the following structures:

wherein, a is as follows ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4 or 5; said b ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2, 3 or 4; the said c ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2 or 3; d is as follows ₂₀₅ Each occurrence is identically or differently selected from 0, 1 or 2; said e ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5 or 6; said f ₂₀₅ Each occurrence is identically or differently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8;

5. The organic electroluminescent device of claim 1, wherein L is ₁₀₁ ～L ₁₀₃ Independently selected from a single bond or one of the structures shown below:

said R is ₁₀₈ At each occurrence, the same orAnd is selected from one of hydrogen atom, deuterium atom, halogen atom, cyano group, substituted or unsubstituted C1-C12 alkyl group.

6. The organic electroluminescent device according to claim 1, wherein the compound represented by formula (I) is selected from one of the following compounds:

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7. The organic electroluminescent device according to claim 1, wherein the compound represented by formula (II) is selected from one of the following compounds:

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8. the organic electroluminescent device of claim 1, wherein the hole transport region comprises two hole transport layers, namely a first hole transport layer and a second hole transport layer, wherein one of the hole transport layers comprises one of the compounds of formula (I) and the other hole transport layer comprises one of the compounds of formula (II).

9. The organic electroluminescent device according to claim 8, wherein the hole transport region further comprises a third hole transport layer, wherein the third hole transport layer comprises one of the compounds represented by formula (I) or formula (II), and is different from the compound contained in the first hole transport layer and the compound contained in the second hole transport layer.

10. The organic electroluminescent device according to claim 1, wherein the hole transport region comprises three hole transport layers, namely, a first hole transport layer, a second hole transport layer and a third hole transport layer, wherein one of the second hole transport layer and the third hole transport layer contains one of the compounds represented by formula (I), the other layer contains one of the compounds represented by formula (II), and the first hole transport layer does not contain the compound represented by formula (I) nor the compound represented by formula (II).