CN114899344B

CN114899344B - Organic electroluminescent device

Info

Publication number: CN114899344B
Application number: CN202210763276.XA
Authority: CN
Inventors: 董秀芹; 孙月; 刘小婷; 陆影
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2022-04-28
Filing date: 2022-06-30
Publication date: 2023-04-07
Anticipated expiration: 2042-06-30
Also published as: CN114899344A

Abstract

The invention provides an organic electroluminescent device, and belongs to the technical field of organic electroluminescence. The organic electroluminescent device provided by the invention can control the injection rate of holes from the hole transport layer to the electron blocking layer, avoids excessive and too fast transmission of holes to the electron blocking layer, solves the problem of accumulation of holes between the electron blocking layer and the light emitting layer, and can improve the condition that a recombination region is close to one side of the electron blocking layer, so that the holes are effectively limited in the light emitting layer to be recombined with electrons to form exciton luminescence, thereby improving the luminous efficiency of the organic electroluminescent device and prolonging the service life of the device. The organic electroluminescent device has good application effect and industrialization prospect.

Description

Organic electroluminescent device

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent device.

Background

An Organic Light-Emitting Diode (OLED) refers to a device in which an Organic semiconductor material and a Light-Emitting material are driven by an electric field and injected and combined with carriers. When a voltage is applied to the device, holes and electrons from the anode and the cathode are injected, respectively, and the injected holes and electrons are recombined in the light-emitting layer to form excitons, and light is emitted when the excitons transition to the ground state. At this time, the OLED may be classified into a fluorescent device in which singlet excitons participate in light emission and a phosphorescent device in which triplet excitons participate in light emission according to the kind of electron spin of the formed excitons.

The device structure of an OLED is similar to a "sandwich", i.e. an organic functional layer is sandwiched between two electrodes. Organic functional layers can be further divided into single-layer, double-layer, three-layer and multilayer device structures according to the number of layers. A single layer structure means that only one layer of light emitting material is contained between two electrodes. The double-layer structure device has one more layer of transmission material to balance the difference of carrier transmission. Tri-layer devices may use both hole transport layers and electron transport layers to further balance the transport of carriers. The multilayer device is formed by adding an injection layer material and/or a blocking layer material outside a three-layer structure to increase the injection of carriers and/or block excessive carriers, so that the exciton recombination region and the light-emitting layer are enabled to be overlapped greatly. Because the functional layers in the multilayer device are mutually matched but independently work, and a plurality of conveniences are provided for the performance optimization of the device, the multilayer structure is a common structure for preparing the OLED device at present.

With the continuous development of OLED products, the requirements for the efficiency, the service life and other properties of the OLED products are higher and higher. The performance of the device mainly depends on the material performance of each film layer and the matching structure of the device, the material direction mainly considers the material mobility, the material stability, the material fluorescence quantum yield (PLQY) and the like, and the matching structure direction mainly considers the energy level matching, the exciton distribution condition, the electron and hole injection and accumulation condition and the like of the adjacent film layers. For the problems of low device efficiency and lifetime, it is currently believed that the main problem is the deviation of the recombination zone between the electron blocking layer/light emitting layer. Therefore, how to limit the exciton recombination region of the device in the light-emitting layer is a problem to be solved urgently at present.

Disclosure of Invention

As holes in the conventional device are too many and are transmitted into the electron blocking layer/luminescent layer too fast, the recombination region of excitons is close to one side of the electron blocking layer, so that the luminescent efficiency and the service life of the device are greatly reduced. In order to solve the above problems, the present invention provides an organic electroluminescent device, which can effectively improve the luminous efficiency and the service life of the organic electroluminescent device.

The invention provides an organic electroluminescent device, which comprises: an anode and a cathode which are oppositely disposed, a light-emitting layer between the anode and the cathode, an electron-blocking layer between the light-emitting layer and the anode, a hole-transporting layer between the electron-blocking layer and the anode, the HOMO level of the electron-blocking layer being equal to or less than the HOMO level of the hole-transporting layer, and the absolute value of the difference between the HOMO level of the hole-transporting layer and the HOMO level of the electron-blocking layer being greater than or equal to 0eV and less than or equal to 0.25eV,

in formula 1, ar is ₁ 、Ar ₂ The same or different is selected from any one of the structures shown below,

ring a is selected from a substituted or unsubstituted spirocyclic structure;

said R is ₁ -R ₅ The same or different ones are selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic ring and substituted or unsubstituted C6-C18 aryl;

a is a ₁ Selected from 0,1, 2,3, 4 or 5; a is a mentioned ₂ Selected from 0,1, 2 or 3; a is a ₃ Selected from 0,1, 2,3 or 4; when two or more R's are present ₁ When two or more R are present ₁ Are the same or different from each other, or two adjacent R ₁ Are connected with each other to form a substituted or unsubstituted ring; when two or more R's are present ₅ When two or more R are present ₅ Are the same or different from each other, or two adjacent R ₅ Are connected with each other to form a substituted or unsubstituted ring;

n is said ₁ Selected from 1,2 or 3;

the R is ₀ Same or different from hydrogen, deuterium, tritium, C1-C6 alkyl, C6-C12 arylAny one of them; said R is ₀ May be substituted by one or more substituents which may be the same or different, and are selected from any one of deuterium, tritium, C1-C12 alkyl, and C6-C12 aryl;

n is ₂ Selected from 0,1, 2,3 or 4; when two or more R's are present ₀ When two or more R are present ₀ Are the same or different from each other, or two adjacent R ₀ Are connected with each other to form a substituted or unsubstituted alicyclic ring;

the above-mentioned

Containing at least one deuterium or tritium;

the Ra and the Rb are the same or different and are any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl and substituted or unsubstituted C6-C12 aryl;

m is said ₁ Selected from 0,1, 2,3 or 4; when two or more Ra are present, two or more Ra are the same or different from each other, or two adjacent Ra are linked to each other to form a substituted or unsubstituted benzene ring;

m is ₂ Selected from 0,1, 2 or 3; when two or more Rb are present, the two or more Rb may be the same or different from each other, or two adjacent Rb may be linked to each other to form a substituted or unsubstituted benzene ring;

ar is ₃ Any one selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl and substituted or unsubstituted C6-C18 aryl;

said L ₁ 、L ₂ The same or different arylene groups are selected from any one of single bond, substituted or unsubstituted C6-C18 arylene groups.

The invention has the beneficial effects that:

according to the organic electroluminescent device provided by the invention, the absolute value delta E1 of the difference between the HOMO value of the hole transport layer and the HOMO value of the electron blocking layer is larger than or equal to 0eV and smaller than or equal to 0.25eV, meanwhile, the structure of the formula 1 is used as a hole transport layer material, the structure of the formula 2 is used as an electron blocking layer material, the injection rate of holes from the hole transport layer to the electron blocking layer can be favorably controlled, the holes are prevented from being excessively and quickly transported to the electron blocking layer, the problem that the holes are accumulated between the electron blocking layer and the light emitting layer is solved, the situation that a composite region is close to one side of the electron blocking layer can be improved, the holes are effectively limited in the light emitting layer to be compounded with electrons to form exciton luminescence, and the exciton composite region moves to the center of the light emitting layer, so that the luminous efficiency of the organic electroluminescent device is improved, and the service life of the device is prolonged.

Drawings

Fig. 1 is a schematic structural diagram of an organic electroluminescent device provided in an embodiment of the present disclosure;

fig. 2 is a schematic diagram of an energy level relationship of an organic electroluminescent device provided by an embodiment of the present disclosure.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. And the embodiments and features of the embodiments may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.

Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The use of "including" or "comprising" and the like in the present application is intended to mean that the items or objects listed before or after the word comprise the elements or objects listed after the word and their equivalents, without excluding other elements or objects. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "inner", "outer", "upper", "lower", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships may also be changed accordingly.

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 their natural isotopic abundance and unnatural abundance.

In the context of the present specification,

means a moiety attached to another substituent.

In the present specification, "" means a moiety linked to another substituent.

In the present specification, when the position of a substituent or attachment site on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional sites of the aromatic ring. For example,

can signify->

And so on.

In the present specification, when a bond at a substituent or attachment site is present throughout two or more rings, it is indicated that it may be attached to either of the two or two rings, in particular to either of the corresponding alternative sites of the rings. For example,

can indicate->

Or->

Can signify->

Can indicate->

Or->

Can indicate->

And so on.

The alkyl group in the present invention refers to a monovalent group formed by subtracting one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group, a branched-chain alkyl group, preferably having 1 to 25 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, and examples may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, and the like, but are not limited thereto.

The alicyclic group in the present invention means a monovalent group formed by removing one hydrogen atom from an alicyclic hydrocarbon molecule, and may be a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, etc., preferably having 3 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, preferably 3 to 12 carbon atoms, preferably 3 to 7 carbon atoms, and examples may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a norbornyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, etc., but are not limited thereto.

The cycloalkyl group in the present invention means a monovalent group formed by subtracting one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, preferably 3 to 12 carbon atoms, preferably 3 to 7 carbon atoms, and examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl and the like, but is not limited thereto.

The cycloalkenyl group in the present invention means a monovalent group formed by dropping one hydrogen atom from a cycloolefin molecule, and preferably has 3 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, preferably 3 to 12 carbon atoms, preferably 3 to 7 carbon atoms, and examples may include cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and the like, but are not limited thereto.

The heterocycloalkyl group in the invention is a univalent group formed by subtracting one hydrogen atom from a heterocycloalkyl molecule, and the heteroatom can be one or more of N, O, S, si and P. Preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, preferably 3 to 12 carbon atoms, preferably 3 to 5 carbon atoms, and examples may include azetidinyl, tetrahydropyrrolyl, tetrahydrofuryl, tetrahydrothienyl, piperidinyl, azepinyl, homopiperidinyl, morpholinyl, thiomorpholinyl, dioxane, and the like, but are not limited thereto.

The aryl group in the present invention refers to a monovalent group obtained by removing one hydrogen atom from an aromatic core carbon of an aromatic hydrocarbon molecule, and may be a monocyclic aryl group, a polycyclic aryl group or a condensed ring aryl group, preferably having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, an indenyl group, a dihydroindenyl group, a dihydronaphthyl group, a tetrahydronaphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylene group, a perylenyl group, and the like, but are not limited thereto.

The fused cyclic group of the alicyclic ring and the aromatic ring in the invention refers to a general name of a monovalent group left by removing one hydrogen atom after the alicyclic ring and the aromatic ring are fused together. Preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, most preferably 7 to 13 carbon atoms, and examples may include benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocycloheptyl, benzocyclopentenyl, benzocycloheptenyl, naphthocyclopropyl, naphthocyclobutyl, naphthocyclopentyl, naphthocyclohexyl, and the like, but are not limited thereto.

The fused cyclic group of the heterocyclic alkane and the aromatic ring is a general name of a monovalent group which is left after the heterocyclic alkane and the aromatic ring are fused together and a hydrogen atom is removed. Preferably having 6 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, most preferably 7 to 13 carbon atoms, and examples may include, but are not limited to, benzoazetidinyl, benzotetrahydropyrrolyl, benzopiperidinyl, benzoazepinyl, naphthotetrahydropyrrolyl, naphthopiperidinyl, phenanthryl tetrahydropyrrolyl, phenanthryl piperidinyl and the like.

The heteroaryl group in the present invention is a general term for a monovalent group obtained by removing one hydrogen atom from a core atom of an aromatic heterocycle composed of carbon and a hetero atom. The hetero atom may be one or more of N, O, S, si, P, may be a monocyclic heteroaryl group or a fused heteroaryl group, preferably having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, most preferably 3 to 8 carbon atoms, and examples may include pyrrolyl, pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, indolyl, quinolyl, isoquinolyl, oxazolyl, thiazolyl, imidazolyl, benzothienyl, benzofuryl, benzoxazolyl, benzothiazolyl, benzimidazolyl, pyridooxazolyl, pyridothiazolyl, pyridoimidazolyl, pyrimidoxazolyl, pyrimidozolyl, pyrimidoimidazolyl, dibenzofuryl, dibenzothienyl, carbazolyl, phenazinyl, quinoxalyl, quinazolinyl, quinoxazolyl, quinozothiazolyl, quinoxalyl, purinyl, purine, 2-purinyl, N-imidazolyl and the like, but are not limited thereto.

The fused cyclic group of the alicyclic ring and the heteroaromatic ring in the invention is a general term for removing one hydrogen atom after the alicyclic ring and the heteroaromatic ring are fused together to leave a monovalent group. Preferably having 5 to 30 carbon atoms, more preferably 5 to 18 carbon atoms, most preferably 5 to 12 carbon atoms, and examples may include pyridocyclopropyl, pyridocyclobutyl, pyridocyclopentyl, pyridocyclohexyl, pyridocycloheptyl, pyrimidocyclopropyl, pyrimidocyclobutyl, pyrimidocyclopentyl, pyrimidocyclohexyl, pyrimidocycloheptyl, dibenzofurocyclopropyl, dibenzofurocyclobutyl, dibenzofurocyclopentyl, dibenzofurocyclohexyl, dibenzofurocycloheptyl, dibenzothienocyclopropyl, dibenzothienocyclobutyl, dibenzothienocyclopentyl, dibenzothienocyclohexyl, dibenzothienocycloheptyl, carbazolocyclopropyl, carbazolocyclobutyl, carbazolocyclopentyl, carbazolocyclohexyl, carbazolocycloheptyl, and the like, but are not limited thereto.

The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from an aromatic nucleus of an aromatic hydrocarbon molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring arylene group, preferably having 6 to 30 carbon atoms, preferably 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenylene group, biphenylene group, terphenylene group, naphthylene group, anthracenylene group, phenanthrenylene group, pyrenylene group, triphenylene group, peryleneene group, and the like, but are not limited thereto.

The alicyclic group in the present invention means a divalent group in which two hydrogen atoms are omitted from an alicyclic hydrocarbon molecule, and may be a cycloalkylene group, a cycloalkenylene group, or the like, preferably having 3 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, preferably 3 to 12 carbon atoms, preferably 3 to 7 carbon atoms, and examples may include, but are not limited to, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, an adamantylene group, a norbornane group, a cyclopropenylene group, a cyclobutenyl group, a cyclopentenylene group, a cyclohexenylene group, a cycloheptenylene group, or the like.

The term "fused ring group" of an alicyclic ring and an aromatic ring as used herein refers to a general term in which an alicyclic ring and an aromatic ring are fused together and then two hydrogen atoms are removed to leave a divalent group. Preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, most preferably 7 to 13 carbon atoms, and examples may include benzocyclobutene, benzocyclopentylene, benzocyclohexylene, benzocycloheptyl, benzocyclopentylene, benzocyclohexylene, benzocycloheptylene, naphthocyclopropyl, naphthocyclobutyl, naphthocyclopentyl, naphthocyclohexyl, and the like, but are not limited thereto.

The "substitution" as referred to herein means that a hydrogen atom in a compound group is replaced with another atom or group, and the position of substitution is not limited.

The "substituted or unsubstituted" of the present inventionBy "is meant not substituted or substituted with one or more substituents selected from the group consisting of: protium, deuterium, tritium, cyano, halogen atom, amino, nitro, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C30 alicyclic ring, substituted or unsubstituted C1-C25 heterocycloalkyl ring, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C30 alicyclic ring and C6-C30 aromatic ring fused ring group, substituted or unsubstituted C1-C25 heterocyclic alkane and C6-C30 aromatic ring fused ring group, substituted or unsubstituted C2-C30 heteroaryl group, substituted or unsubstituted C3-C25 alicyclic ring and C2-C30 heteroaromatic ring fused ring group, substituted or unsubstituted C6-C30 arylamine group, substituted or unsubstituted C6-C30 aryloxy group, preferred is protium, deuterium, tritium, halogen atom, cyano group, C1-C12 alkyl group, C3-C18 alicyclic group, C6-C25 aryl group, C2-C25 heteroaryl group, and specific examples may include protium, deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, cyclopentenyl group, cyclohexenyl group, benzocyclobutenyl group, benzocyclopentyl group, benzocyclohexyl group, benzocyclopentenyl group, benzocyclohexenyl group, phenyl group, tolyl group, mesityl group, pentadeuterated phenyl group, biphenyl group, naphthyl group, anthracenyl group, phenanthryl group, benzophenanthryl group, pyrenyl group, triphenylenyl group,

A phenyl group, a perylene group, a fluoranthenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a 9-methyl-9-phenylfluorenyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a spirobifluorenyl group, a carbazoloindolyl group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzotriazolyl group, a benzimidazolyl group, a pyridooxazolyl group, a pyridothiazolyl group, a pyridoimidazolyl group, a pyrimido oxazolyl group, a pyrimido-thiazolyl group, a pyrimido-imidazolyl group, a quinolyl group, an isovaleryl group, a pyrimido-fluorenyl group, a pyrimido-oxazolyl group, a pyrimido group, aQuinolyl, quinoxazolyl, quinothiazolyl, quinoimidazolyl, phenothiazinyl, phenoxazinyl, acridinyl, and the like, but are not limited thereto. Or when the substituents are two or more, adjacent substituents may be bonded to form a ring; when the substituents are two or more, the substituents may be the same as or different from each other.

The linking to form a substituted or unsubstituted ring in the present invention means that two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:

in the present invention, the ring to be connected may be a five-membered ring or a six-membered ring or a fused ring, and examples may include benzene, pyridine, pyrimidine, naphthalene, fluorene, cyclopentene, cyclohexene, cyclopentane, cyclohexane acene, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but are not limited thereto.

The invention provides an organic electroluminescent device, which comprises: an anode and a cathode disposed opposite to each other, a light-emitting layer between the anode and the cathode, an electron-blocking layer between the light-emitting layer and the anode, and a hole-transporting layer between the electron-blocking layer and the anode, the HOMO level of the electron-blocking layer being equal to or less than the HOMO level of the hole-transporting layer, and the absolute value of the difference between the HOMO level of the hole-transporting layer and the HOMO level of the electron-blocking layer being greater than or equal to 0eV and less than or equal to 0.25eV.

Preferably, the absolute value of the difference between the HOMO value of the hole transport layer and the HOMO value of the electron blocking layer is greater than or equal to 0.03eV and less than or equal to 0.24eV.

An organic electroluminescent device according to the present invention, schematically illustrated in fig. 1 and 2, includes: the organic electroluminescent device comprises an anode 1 and a cathode 2 which are oppositely arranged, a luminescent layer 3 positioned between the anode 1 and the cathode 2, wherein the luminescent layer 3 comprises a host material and a doping material, an electron blocking layer 4 positioned between the luminescent layer 3 and the anode 1, and a hole transport layer 5 positioned between the electron blocking layer 4 and the anode 1, the HOMO energy level of the electron blocking layer 4 is equal to or less than the HOMO energy level of the hole transport layer 5, the absolute value of the difference between the HOMO value of the hole transport layer 5 and the HOMO value of the electron blocking layer 4 is greater than or equal to 0eV and less than or equal to 0.25eV, and the energy level relationship not only helps to control the injection rate of holes from the hole transport layer 5 to the electron blocking layer 4, but also helps to transport holes on the luminescent layer 3, so that the holes are effectively limited to be combined with electrons in the luminescent layer 3 to form exciton luminescence, and a recombination region moves to the center of the luminescent layer 3. The combined action of the two aspects effectively avoids the accumulation of the holes at the interface of the luminescent layer 3 and the electron blocking layer 4, and enables the holes to better move towards the interior of the luminescent layer 3, thereby improving the efficiency and the service life of the organic electroluminescent device.

The material of the hole transport layer of the present invention is selected from the structure shown in formula 1 below,

ring a is selected from a substituted or unsubstituted spirocyclic structure;

the R is ₁ -R ₅ The same or different is selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic ring and substituted or unsubstituted C6-C18 aryl;

a is a ₁ Selected from 0,1, 2,3, 4 or 5; a is a ₂ Selected from 0,1, 2 or 3; a is a mentioned ₃ Selected from 0,1, 2,3 or 4; when two or more R's are present ₁ When two or more R are present ₁ Are the same or different from each other, or two adjacent R ₁ Are connected with each other to form a substituted or unsubstituted ring; when two or more R's are present ₅ When two or more R are present ₅ Are the same or different from each other, or two adjacent R ₅ Are connected with each other to form a substituted or unsubstituted ring;

n is ₁ Selected from 1,2 or 3;

the R is ₀ The same or different is selected from any one of hydrogen, deuterium, tritium, C1-C6 alkyl and C6-C12 aryl; the R is ₀ May be substituted with one or more substituents which may be the same or different, and are selected from any one of deuterium, tritium, C1-C12 alkyl, and C6-C12 aryl;

the above-mentioned

Containing at least one deuterium or tritium;

m is ₁ Selected from 0,1, 2,3 or 4; when two or more Ra are present, the two or more Ra are the same or different from each other, or two adjacent Ra are linked to each other to form a substituted or unsubstituted benzene ring;

Preferably, the

Selected from any one of the structures shown below,

the R is ₀ 、R ₆ The same or different is selected from any one of hydrogen, deuterium, tritium, methyl, ethyl, isopropyl, tertiary butyl, adamantyl, norbornyl, phenyl, biphenyl and naphthyl; said R is ₀ May be substituted with one or more substituents which may be the same or different, and are selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl; the R is ₆ May be substituted with one or more substituents which may be the same or different, and are selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl;

n is ₃ The same or different is selected from 0,1, 2,3 or 4; n is ₄ Identical or different from 0,1, 2 or 3; when two or more R's are present ₀ When two or more R are present ₀ Are the same or different from each other;

b is ₁ The same or different is selected from 0,1 or 2; b is ₂ The same or different is selected from 0,1, 2,3 or 4; b is ₃ The same or different is selected from 0,1, 2,3, 4,5 or 6; b is ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; b is described ₅ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; b is described ₆ Identical or different from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; when two or more R's are present ₆ When two or more R are present ₆ The same or different from each other.

Preferably, the

Selected from any one of the structures shown below,

the R is ₀ 、R ₆ Any one of hydrogen, deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, biphenyl and naphthyl which are the same or different; said R is ₀ May be substituted with one or more substituents which may be the same or different, and are selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl; the R is ₆ May be substituted with one or more substituents which may be the same or different, and are selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl;

n is ₃ Identical or different from 0,1, 2,3 or 4; n is ₄ The same or different is selected from 0,1, 2 or 3; when two or more R's are present ₀ When two or more R are present ₀ Are the same or different from each other;

b is ₁ The same or different is selected from 0,1 or 2; b is ₂ The same or different is selected from 0,1, 2,3 or 4; b is ₃ The same or different is selected from 0,1, 2,3, 4,5 or 6; b is ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; b is ₅ Identical or different from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; b is ₆ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; when two or more R's are present ₆ When two or more R are present ₆ Are the same or different from each other;

said x ₁ The same or

different optionsFrom

1,2, 3 or 4; said x ₂ The same or different is selected from 1,2, 3,4, 5 or 6; said x ₃ The same or different is selected from 1,2, 3,4, 5, 6,7 or 8; x is said ₄ The same or different is selected from 1,2, 3,4, 5, 6,7,8, 9 or 10; said x ₅ Identical or different from 1,2, 3,4, 5, 6,7,8, 9,10, 11 or 12; said x ₆ The same or different is selected from 1,2, 3,4, 5, 6,7,8, 9,10, 11, 12, 13 or 14.

Preferably, the

At least two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty-one, twenty-two, twenty-three, twenty-four, twenty-five deuterium or tritium.

Preferably, ar is ₁ 、Ar ₂ The same or different is selected from any one of the structures shown below,

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said R is ₁ 、R ₅ 、R ₇ Any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, biphenyl and terphenyl, which are the same or different; the R is ₁ May be substituted by one or more substituents which may be the same or different and are selected from any one of methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl and phenyl; the R is ₅ May be substituted by one or more substituents, which may be the same or different, selected from methyl, ethyl, isopropyl, tert-butylAny one of a phenyl group, an adamantyl group, a norbornyl group and a phenyl group; said R is ₇ May be substituted by one or more substituents which may be the same or different and are selected from any one of methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl and phenyl;

a is a ₁ The same or different is selected from 0,1, 2,3, 4 or 5; a is a mentioned ₂ The same or different is selected from 0,1, 2 or 3; a is a mentioned ₃ The same or different is selected from 0,1, 2,3 or 4; a is a mentioned ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; a is a ₅ Identical or different from 0,1, 2,3, 4,5 or 6; a is a ₆ Identical or different from 0,1, 2,3, 4,5, 6,7 or 8; a is a ₇ Identical or different from 0,1, 2,3, 4,5, 6,7,8 or 9; when two or more R's are present ₁ When two or more R are present ₁ Are the same or different from each other; when two or more R's are present ₅ When two or more R are present ₅ Are the same or different from each other;

q is a number of ₁ The same or different is selected from 0,1, 2,3, 4 or 5; q is a number of ₂ Identical or different from 0,1, 2,3 or 4; q is a radical of ₃ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; q is a number of ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; q is a number of ₅ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; q is a radical of ₆ The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; q is a radical of ₇ The same or different is selected from 0,1, 2,3, 4,5 or 6; when two or more R's are present ₇ When two or more R are present ₇ The same or different from each other.

Preferably, the

Is selected from any one of the structures shown below>

The Ra, rb and R ₈ Any one of hydrogen, deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl and naphthyl; the Ra may be substituted by one or more substituents which may be the same or different, and are selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, naphthyl; the Rb may be substituted with one or more substituents which may be the same or different, selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, naphthyl; said R is ₈ May be substituted with one or more substituents which may be the same or different, selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, naphthyl;

m is said ₁ Selected from 0,1, 2,3 or 4; when two or more Ra are present, the two or more Ra are the same or different from each other, or two adjacent Ra are linked to each other to form a substituted or unsubstituted benzene ring;

said p is ₁ The same or different is selected from 0,1, 2,3 or 4; said p is ₂ Identical or different from 0,1, 2,3, 4,5 or 6; said p is ₃ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; said p is ₄ Identical or different from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; said p is ₅ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; said p is ₆ The same or different is selected from 0,1, 2,3, 4 or 5; said p is ₇ The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; said p is ₈ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8 or 9; said p is ₉ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10 or 11; said p is ₁₀ The same or different is selected from 0,1, 2 or 3; when two or more R's are present ₈ When two or more R are present ₈ The same or different from each other.

Preferably, said L ₁ 、L ₂ The same or different is selected from a single bond or any one of the structures shown below,

the R is ₉ Any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, biphenyl and naphthyl which are the same or different; the R is ₉ May be substituted with one or more substituents which may be the same or different, and are selected from any one of methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl;

v is ₁ Identical or different from 0,1, 2,3 or 4; v is ₂ The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; when two or more R's are present ₉ When two or more R are present ₉ The same or different from each other.

Preferably, the material of the hole transport layer is selected from any one of the structures shown below,

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preferably, the organic electroluminescent device of the present invention comprises: the light-emitting diode comprises an anode and a cathode which are oppositely arranged, a light-emitting layer positioned between the anode and the cathode, an electron blocking layer positioned between the light-emitting layer and the anode, a hole transport layer positioned between the electron blocking layer and the anode, and an electron transport region positioned between the light-emitting layer and the cathode.

The electron transport region comprises at least one of a hole blocking layer, an electron transport layer and an electron injection layer.

Preferably, the electron transport region of the present invention includes an electron transport layer.

Preferably, the electron transport region of the present invention includes an electron injection layer.

Preferably, the electron transport region of the present invention includes an electron transport layer and an electron injection layer.

Preferably, the electron transport region according to the present invention includes a hole blocking layer and an electron injection layer.

Preferably, the electron transport region according to the present invention includes a hole blocking layer and an electron transport layer.

Preferably, the electron transport region according to the present invention includes a hole blocking layer, an electron transport layer, and an electron injection layer.

Preferably, the organic electroluminescent device of the present invention further comprises: a hole injection layer located between the anode and the hole transport layer.

The structure of the organic electroluminescent device of the present invention having the above hole transport layer is further described with reference to fig. 1 and 2. As shown in fig. 1, the organic electroluminescent device according to the present invention may further include: a hole injection layer 6 between the anode 1 and the hole transport layer 5, a hole blocking layer 7 between the light emitting layer 3 and the cathode 2, an electron transport layer 8 between the hole blocking layer 7 and the cathode 2, and an electron injection layer 9 between the cathode 2 and the electron transport layer 8.

The present invention is not particularly limited to the thickness of each organic layer of the organic electroluminescent device, and may be any thickness commonly used in the art.

In the organic electroluminescent device according to the present invention, preferably, the thickness of the hole injection layer is 5nm to 20nm, the thickness of the hole transport layer is 80nm to 150nm, the thickness of the hole blocking layer is 5nm to 20nm, the thickness of the electron transport layer is 20nm to 50nm, and the thickness of the electron injection layer is 1nm to 10nm.

The anode according to the present invention preferably uses a high work function material (work function greater than 4.0 eV) capable of promoting hole injection into other functional layers, and specific examples of the anode material that may be used in the present invention may include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO); combinations of metals and oxides, such as indium tin oxide-silver-indium tin oxide (ITO-Ag-ITO); conductive polymers such as poly (3-methylthiophene), polypyrrole, polyaniline, poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDT), and the like, but are not limited thereto.

The hole injection layer of the present invention preferably uses a material having a good hole accepting ability. Specific examples of the hole injection layer material that can be used in the present invention may include metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, phthalocyanine compounds, benzidine compounds, phenazine compounds, and the like, such as copper phthalocyanine (CuPc), titanyl phthalocyanine, N '-diphenyl-N, N' -di- [4- (N, N-diphenylamine) phenyl ] benzidine (npnpnpb), N '-tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), biquinoxalino [2,3-a:2',3'-c ] phenazine (HATNA), 4' -tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN), 4', 4' -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but is not limited thereto.

The electron blocking layer of the present invention preferably uses a material having an absolute value of a difference from the HOMO value of the hole transport layer of 0.07eV or more and 0.35eV or less, and specific examples may include triarylamine derivatives, spirofluorene derivatives, furan derivatives, and the like, such as TPD, NPB, N4-bis ([ 1,1 '-biphenyl ] -4-yl) -N4' -phenyl N4'- [1,1':4', 1' -terphenyl ] -4-yl- [1,1' -biphenyl ] -4,4' -diamine, N- ([ 1,1' -diphenyl ] -4-yl) -N- (9, 9-dimethyl-9H-furan-2-yl) -9,9' -spirobifluorene-2-amine, N-bis ([ 1,1' -biphenyl ] -4-yl) -3' - (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine, triamine compounds described in the present invention, and the like, but are not limited thereto. Preferably, the material of the electron blocking layer according to the present invention is selected from the structure shown in formula 2 below,

in the formula 2, ar _a 、Ar _b The same or different structures are selected from any one of the structures shown in the chemical formulas I to IV,

ring B is selected from a substituted or unsubstituted spirocyclic structure;

the R is _c -R _g Any one of the same or different groups selected from hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic ring and C6-C18 aromatic ring fused ring group, and substituted or unsubstituted C6-C18 aryl;

m is _a Selected from 0,1, 2 or 3; m is _b Selected from 0,1, 2 or 3 or 4; when two or more R's are present _c When two or more R are present _c Are the same or different from each other, or two adjacent R _c Are connected with each other to form a substituted or unsubstituted ring; when two or more R's are present _d When two or more R are present _d Are the same or different from each other, or two adjacent R _d Are connected with each other to form a substituted or unsubstituted ring;

ar is _c Selected from any one of the structures shown below,

the R is _h Any one of the same or different selected from hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic ring, C6-C18 aromatic ring fused ring group, and substituted or unsubstituted C6-C18 aryl;

n is _a The same or different is selected from 0,1, 2,3, 4 or 5; n is _b The same or different is selected from 0,1, 2,3 or 4; n is _c Identical or different from 0,1, 2 or 3; when two or more R's are present _h When two or more R are present _h Are the same or different from each other, or adjacent R _h Are connected with each other to form a substituted or unsubstituted ring;

L _a ～L _c the same or different one selected from single bond, substituted or unsubstituted C6-C18 arylene;

the above-mentioned

Containing at least one deuterium or tritium.

Preferably, ar is _a 、Ar _b The same or different is selected from any one of the structures shown below,

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the R is _c 、R _d 、R _i Any one of hydrogen, deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, benzocyclopropyl, benzocyclobutenyl, benzocyclopentyl, and benzocyclohexyl, which may be the same or different; the R is _c May be substituted by one or more substituents which may be the same or different and are selected from any one of methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl and phenyl; the R is _d May be substituted by one or more substituents which may be the same or different and are selected from methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornylAny one of phenyl and phenyl; the R is _i May be substituted by one or more substituents which may be the same or different and are selected from any one of methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl and phenyl;

m is _a The same or different is selected from 0,1, 2 or 3; m is _b Identical or different from 0,1, 2,3 or 4; m is _c The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; m is _d The same or different is selected from 0,1, 2,3, 4,5 or 6; m is _e Identical or different from 0,1, 2,3, 4,5, 6,7 or 8; m is _f The same or different is selected from 0,1, 2,3, 4,5, 6,7,8 or 9; m is _g The same or different is selected from 0,1, 2,3, 4 or 5; when two or more R's are present _c When two or more R are present _c Are the same or different from each other; when two or more R's are present _d When two or more R are present _d Are the same or different from each other;

v is _a The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; v is _b The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; v is _c The same or different is selected from 0,1, 2,3, 4 or 5; v is _d The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10 or 11; v is _e The same or different is selected from 0,1, 2,3, 4,5, 6,7,8 or 9; v is _f The same or different is selected from 0,1, 2,3 or 4; v is _g The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; v is _h Identical or different from 0,1, 2,3, 4,5 or 6; v is _i The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; when two or more R's are present _i When two or more R are present _i The same or different from each other.

Preferably, ar is _c Selected from any one of the structures shown below,

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said R is _h Any one of hydrogen, deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl and naphthyl;

the R is _h May be substituted with one or more substituents selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl;

n is _a The same or different is selected from 0,1, 2,3, 4 or 5; n is _b The same or different is selected from 0,1, 2,3 or 4; n is said _c The same or different is selected from 0,1, 2 or 3; n is said _d The same or different is selected from 0,1 or 2; n is said _e The same or different is selected from 0,1, 2,3, 4,5 or 6; n is _f Identical or different from 0,1, 2,3, 4,5, 6,7 or 8; n is _g The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; when two or more R's are present _h When two or more R are present _h The same or different from each other.

Preferably, ar is _c Selected from any one of the structures shown below,

said y ₁ The same or different ones are selected from 0,1,2.3, 4 or 5; said y ₂ The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; y is ₃ Identical or different from 0,1, 2,3, 4,5, 6,7,8 or 9; said y ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10 or 11; said y ₅ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11, 12 or 13; said y ₆ The same or different is selected from 0,1, 2,3 or 4;

the R is _h Any one of hydrogen, deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl and naphthyl;

said R is _h May be substituted with one or more substituents selected from any one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl;

n is _a The same or different is selected from 0,1, 2,3, 4 or 5; n is said _b The same or different is selected from 0,1, 2,3 or 4; n is said _c The same or different is selected from 0,1, 2 or 3; n is _d The same or different is selected from 0,1 or 2; n is _e The same or different is selected from 0,1, 2,3, 4,5 or 6; n is _f The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; n is _g The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; when two or more R's are present _h When two or more R are present _h The same or different from each other.

Preferably, said L _a ～L _c The same or different is selected from single bonds or any one of the structures shown as the following,

the R is _k The same or different is selected from hydrogenAny one of deuterium, tritium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, benzocyclopropyl, benzocyclobutenyl, benzocyclopentyl, and benzocyclohexyl; the R is ₉ May be substituted with one or more substituents which may be the same or different and are selected from any one of methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl;

k is ₁ The same or different is selected from 0,1, 2,3 or 4; k is ₂ The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; when two or more R's are present _k When two or more R are present _k Are the same or different from each other, or two adjacent R _k Are linked to each other to form a substituted or unsubstituted ring.

Preferably, the

Preferably, the material of the electron blocking layer according to the present invention is selected from any one of the following structures,

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the light emitting layer of the present invention is a layer in which holes and electrons meet to form excitons, and the color of light emitted from the organic electroluminescent device may be changed depending on the material constituting the light emitting layer. The light emitting layer includes a host material and a dopant material, and the mixing ratio thereof may be appropriately adjusted within a range known in the art. With the hairThe light emitting layer may include 70 to 99.9 parts by weight of a host material and 0.1 to 30 parts by weight of a dopant material, based on the entire weight of the light layer. Preferably, in the case where the light emitting layer is blue fluorescent, green fluorescent, or red fluorescent, the light emitting layer may include 80 to 99.9 parts by weight of the host material and 0.1 to 20 parts by weight of the dopant material. Preferably, in the case where the light emitting layer is blue fluorescent, green fluorescent, or red phosphorescent, 70 to 99 parts by weight of the host material and 1 to 30 parts by weight of the dopant material may be included. The host material included in the light-emitting layer of the present invention may be any known host material in the art, and may be an alkali metal complex compound, an alkaline earth metal complex compound, a condensed aromatic ring derivative, or the like. Specific examples of the host material usable in the present invention may include one or a combination of more than one of an aluminum complex, a beryllium complex, an anthracene derivative, a pyrene derivative, a triphenylene derivative, a carbazole derivative, a dibenzofuran derivative, and a dibenzothiophene derivative, such as 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -ADN), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1 ″,4 ″,1"' -tetrabiphenyl]-4,4' -diamino (4 PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like, but are not limited thereto. The doping material included in the light emitting layer according to the present invention may be a known doping material, and may be a red doping material, a green doping material, and a blue doping material. The red doped material can be one or more of octaethylporphyrin platinum (II) (PtOEP), tris (2-phenylisoquinoline) iridium (Ir (piq) 3), bis (2- (2 '-benzothienyl) -pyridine-N, C3') (acetylacetone) iridium) (Btp 2Ir (acac)) or a combination thereof; the green dopant material may be tris (2-phenylpyridine) iridium (Ir (ppy) 3), bis (2-phenylpyridine) (acetylacetone) iridium (III) (Ir (ppy) ₂ (acac)), tris (2- (4-tolyl) phenylpyridine) iridium (Ir (mppy) 3), 10- (2-benzothiazolyl) -1, 7-tetramethyl-2, 3,6,7, -tetrahydro-1H, 5H,11H- [1]Benzopyrano [6,7,8-ij]One or more of quinolizin-11-one (C545T)(ii) a The blue doping material can be one or more of bis [3, 5-difluoro-2- (2-pyridyl) phenyl (picolinyl) iridium (III) (F2 Irpic), 4' -bis (2, 2' -diphenylethylene-1-yl) biphenyl (DPVBi), 4' -bis (4-diphenylaminostyryl) biphenyl (DPAVBi) and 2,5,8, 11-tetra-tert-butylperylene (TBPe).

The light-emitting layer according to the present invention may be a single layer made of one substance, a single layer made of a plurality of substances different from each other, or a multilayer having two or more layers each made of a different substance. When the light-emitting layer is a plurality of layers, the organic electroluminescent element can emit light of a plurality of colors.

The organic electroluminescent device according to the present invention may have a plurality of light emitting layer stacks including at least one of the light emitting layers. The plurality of light emitting layers included in the light emitting layer stack may each include a light emitting layer emitting light of a different color from each other or a light emitting layer emitting light of the same color. That is, the emission color may vary depending on the substance constituting the light emitting layer. For example, the plurality of light emitting layer stacks may include a substance emitting light of blue, green, red, yellow, white, or the like, and may be formed using a phosphorescent or fluorescent substance. At this time, the colors emitted by the light emitting layers may be in a complementary color relationship with each other. In addition, the color may be selected according to a combination of colors that can emit white light.

The hole blocking layer of the present invention is preferably made of a material having a high hole blocking ability and a suitable HOMO/LUMO level. Specific examples of the hole blocking layer material that can be used in the present invention may include imidazoles, triazoles, phenanthroline derivatives, and the like, such as 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), and the like, but are not limited thereto.

The electron transport layer according to the present invention preferably uses a material having a strong electron withdrawing ability and a low HOMO and LUMO level, and specific examples of the electron transport layer material that may be used in the present invention may include imidazoles, triazoles, phenanthroline derivatives, quinolines, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalene-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (HNBphen), 8-hydroxyquinoline-lithium, and the like, but are not limited thereto.

The electron injection layer according to the present invention preferably uses a material having a small potential barrier to an adjacent organic transport material while having an effect of injecting electrons from a cathode, and specific examples of the electron injection layer material that can be used in the present invention may include alkali metal salts (such as LiF, csF), alkaline earth metal salts (such as MgF) ₂ ) Metal oxides (e.g. Al) ₂ O ₃ 、MoO ₃ ) But is not limited thereto.

The cathode according to the present invention preferably uses a low work function material capable of facilitating electron injection into the organic layer, and specific examples of the cathode material that can be used in the present invention may include metals such as aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof; multilayer metallic materials, e.g. LiF/Al, mg/Ag, li/Al, liO ₂ /Al、BaF ₂ Al, etc., but are not limited thereto.

The organic electroluminescent device according to the present invention may further include a capping layer, and the capping layer according to the present invention preferably uses a material capable of improving optical coupling, and specific examples of the capping layer material that may be used in the present invention may include, but are not limited to, arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, and the like.

The organic electroluminescent device according to the present invention may further include a substrate, and the substrate according to the present invention may preferably use a material that does not change when forming an electrode and other functional layers, and specific examples of the substrate material that may be used in the present invention may include glass, quartz, plastic, polymer film, silicon, and the like, but are not limited thereto. The substrate may be retained in a light-emitting device or an electronic apparatus using the organic electroluminescent device of the present invention, or may not be retained in a final product and may function as a support only in a manufacturing process of the organic electroluminescent device.

However, the structure of the organic electroluminescent device according to the present invention is not limited thereto. The organic electroluminescent device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, part of organic layers can be added or omitted, and the organic layers with the same function can be made into a laminated structure with more than two layers.

The light-emitting type of the organic electroluminescent device can be a top-emitting device or a bottom-emitting device, and the difference between the light-emitting type and the bottom-emitting type is that the light-emitting direction of the device is emitted through the substrate or is emitted in a direction deviating from the substrate. For bottom-emitting devices, the light-emitting direction of the device is through the substrate emission; for a top-emitting device, the light-emitting direction of the device is the direction away from the substrate.

The structure of the organic electroluminescent device can be a positive structure or an inverted structure, and the difference between the positive structure and the inverted structure lies in that the manufacturing sequence of organic layers is different, and specifically comprises the following steps: the positive structure is formed by sequentially forming a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, a hole transport layer, a hole injection layer and an anode on a substrate, and the negative structure is formed by sequentially forming an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode on a substrate.

The organic electroluminescent device of the present invention may be any one of a vacuum evaporation method, a spin coating method, a vapor deposition method, a blade coating method, a laser thermal transfer method, an electrospray coating method, a slit coating method, and a dip coating method.

The organic electroluminescent device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.

Preparation and characterization of the Compounds

The method for preparing the structure represented by formula 1 of the present invention is not particularly limited, and conventional methods well known to those skilled in the art may be employed.

For example, carbon-nitrogen coupling reaction, carbon-carbon coupling reaction, etc., the structure represented by formula 1 of the present invention can be prepared by the following synthetic route.

The method for preparing the structure represented by formula 2 of the present invention is not particularly limited, and conventional methods well known to those skilled in the art may be used. For example, carbon-nitrogen coupling reaction, carbon-carbon coupling reaction, etc., the structure represented by formula 2 of the present invention can be prepared by the following synthetic route.

Said X is _a Identical or different from halogen, for example Cl, br, I.

Description of raw materials, reagents and characterization equipment:

the present invention is not limited to any particular source of the starting materials and reagents used in the following examples, and they may be commercially available products or prepared by methods known to those skilled in the art. The raw materials and reagents used in the invention are all pure reagents.

The mass spectrum uses a British Watts G2-Si quadrupole rod series flight time high resolution mass spectrometer, and chloroform is used as a solvent;

the element analysis uses a Vario EL cube type organic element analyzer of Elementar company in Germany, and the sample mass is 5-10 mg;

synthesis example 1 Synthesis of intermediate 3-A

Under the protection of nitrogen, 3-a (80.00mmol, 22.97g), 3-b (80.00mmol, 22.95g), palladium tetratriphenylphosphine (1.60mmol, 1.85g), potassium carbonate (156.00mmol, 21.56g), 450mL of toluene, 150mL of ethanol, and 150mL of water were added to a reaction flask, and the mixture was stirred, and the system was heated under reflux for 3.5 hours. After the reaction was completed, cooled to room temperature, water was added, extracted with dichloromethane, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed with toluene/ethanol =4:1 to give intermediate 3-a (26.07 g, 81% yield); the purity of the solid was 99.75% by HPLC. Mass spectrum m/z:401.0723 (theoretical value: 401.0717).

Synthesis example 2 Synthesis of intermediate 75-A

The same procedure was repeated except for replacing 3-a in Synthesis example 1 with an equimolar amount of 75-a and 3-b with an equimolar amount of 75-b to give intermediate 75-c (22.48 g, yield 80%) having a purity of 99.63% by HPLC. Mass spectrum m/z:281.0923 (theoretical value: 281.0909).

Intermediate 75-c (60mmol, 16.86g) was dissolved in 600ml of NMP, and then compound 75-d (78mmol, 15.37g), sodium sulfate (60mmol, 8.4g), potassium carbonate (60mmol, 8.4g) and copper (18mmol, 1.2g) were added and reacted at 200 ℃ for 12 hours. Cooling to room temperature, removal of the solvent by distillation under reduced pressure, washing with distilled water, extraction with dichloromethane, drying of the organic phase with anhydrous magnesium sulfate, and removal of the solvent by distillation under reduced pressure, purification by distillation with toluene/ethanol =5:1 recrystallisation for purification afforded intermediate 75-a (17.87 g,75% yield) in 99.60% purity by HPLC. Mass spectrum m/z:397.1542 (theoretical value: 397.1535).

Synthesis example 3 Synthesis of intermediate 107-A

The same procedure was repeated except for replacing 3-a in Synthesis example 1 with an equimolar amount of 107-e and replacing 3-b with an equimolar amount of 107-f to obtain intermediate 107-d (17.29 g, yield 78%) having a purity of 99.53% by HPLC. Mass spectrum m/z:277.0519 (theoretical value: 277.0514).

The 75-d in Synthesis example 2 was replaced with an equimolar amount of 107-d and the other steps were the same to give intermediate 107-A (21.52 g, yield 75%) having a purity of 99.41% by HPLC. Mass spectrum m/z:478.2154 (theoretical value: 478.2162).

Synthesis example 4 Synthesis of intermediate 191-A

The 75-d in Synthesis example 2 was replaced with an equimolar amount of 191-d and the other steps were the same to give intermediate 191-A (22.69 g, yield 77%) having a purity of 99.69% by HPLC. Mass spectrum m/z:491.2322 (theoretical value: 491.2318).

The following intermediates were prepared according to the preparation method of synthesis example 1, with the following raw materials and intermediates:

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[ Synthesis example 5] Synthesis of intermediate 3-B

Under the protection of nitrogen, toluene (150 mL), 3-A (40.00mmol, 16.04g), 3-g (40.00mmol, 10.14g), palladium acetate (0.60mmol, 0.13g), sodium tert-butoxide (80.00mmol, 7.69g) and tri-tert-butylphosphine (2.40mmol, 0.49g) were added in this order to a reaction flask, and the mixture was dissolved by stirring and refluxed for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water was added, extraction was performed with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, and the residue was purified by filtration with toluene/methanol =10:1 recrystallization purification gave 3-B (24.12 g, 82% yield) with a purity of 99.59% by HPLC. Mass spectrum m/z:490.2355 (theoretical value: 490.2347)

The following intermediates were prepared according to the preparation method of synthesis example 5, with the following raw materials and intermediates being as specified in the following table:

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synthesis example 6 Synthesis of Compounds 1 to 3

Under the protection of nitrogen, toluene (150 mL), 3-B (20.00mmol, 14.37g), 3-h (26.00mmol, 8.16g), dibenzylideneacetone dipalladium (0.20mmol, 0.19g), sodium tert-butoxide (40.00mmol, 3.85g) and tri-tert-butylphosphine (1.60mmol, 0.33g) are added into a reaction bottle in sequence, stirred and dissolved, and the reaction is refluxed for 6.5 hours. Inverse directionAfter completion, the reaction solution was cooled to room temperature, water was added, extraction was performed with chloroform, the organic phase was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and recrystallization was performed with toluene to obtain compound 1-3 (9.40 g, yield 83%) with a solid purity of 99.95% by HPLC. Mass spectrum m/z:566.2668 (theoretical value: 566.2660). Theoretical element content (%) C ₄₂ H ₂₆ D ₄ N ₂ : c,89.01; h,6.05; and N,4.94. Measured elemental content (%): c,89.03; h,6.02; and N,4.95.

The following compounds were prepared according to the preparation method of synthesis example 6, with corresponding substitution of the intermediate and starting materials:

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synthetic example 7: preparation of intermediate c-2-107

Under the protection of nitrogen, adding n into the reaction bottle in sequence ₁ -2-107(13.89g，60mmol)，n ₂ -2-107 (15.00g, 63mmol), potassium carbonate (12.44g, 90mmol), pd (PPh) ₃ ) ₄ (0.69g, 0.60mmol), 400mL of a toluene/ethanol/water (3. After the reaction is finished, cooling to room temperature, adding toluene, separating each phase,washing the toluene phase with distilled water for three times, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling, crystallizing, filtering, recrystallizing the obtained solid with toluene to obtain intermediate c-2-107 (16.14 g, yield 78%), and purity of the solid is not less than 99.37% by HPLC. Mass spectrum m/z:344.1349 (theoretical value: 344.1332).

Synthesis example 8: preparation of intermediate c-2-201

Intermediate n ₂ -2-201 preparation:

under the protection of nitrogen, adding n into the reaction bottle in sequence ₃ -2-201 (24.95g, 90.00mmol), pinacol diboron (24.12g, 95.00mmol), pd (dppf) Cl ₂ (0.66g, 0.90mmol), KOAc (15.70g, 160.00mmol), 500mL DMF, refluxing and heating for 4 hours, adding distilled water after the reaction is finished, extracting with dichloromethane, washing the organic phase with distilled water for three times, standing and separating, collecting the organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling and crystallizing, filtering, recrystallizing the obtained solid with toluene to obtain an intermediate n ₂ -2-201 (22.18 g, yield 76%); HPLC purity is more than or equal to 98.68 percent. Mass spectrum m/z:324.2186 (theoretical value: 324.2199).

Preparation of intermediate c-2-201:

according to the preparation method of Synthesis example 1, n is added in equimolar amounts ₁ -2-107、n ₂ -2 to 107 are each replaced by equimolar amounts of n ₁ -2-201、n ₂ 2-201 to obtain intermediate c-2-201 (13.90g, 75%) with an HPLC purity of ≧ 99.58%. Mass spectrum m/z:308.1283 (theoretical value: 308.1270).

Synthetic example 9: preparation of intermediate c-2-245

According to the preparation method of Synthesis example 7, n is added in equimolar amounts ₁ -2-107、n ₂ -2 to 107 are each replaced by equimolar amounts of n ₁ -2-245、n ₂ 2-245 to obtain intermediate c-2-245 (16.03 g) with HPLC purity ≧ 99.43%. Mass spectrum m/z:360.1632 (theoretical value: 360.1645).

Synthetic example 10: intermediate c ₁ Preparation of (E) -2-289

According to the preparation method of Synthesis example 7, n is added in equimolar amounts ₁ -2-107、n ₂ -2 to 107 are each replaced by equimolar amounts of n ₁ -2-107、n ₂ -2-289 to give intermediate c ₁ -2-289 (11.08 g), HPLC purity ≧ 99.58%. Mass spectrum m/z:233.1003 (theoretical value: 233.1020).

Synthetic example 11: preparation of Compounds 2 to 6

Preparation of intermediate M-2-6:

adding m into the reaction bottle in sequence under the protection of nitrogen ₁ -2-6 (28.81g, 150.00mmol), pinacol diboron (40.12g, 158.00mmol), pd (dppf) Cl ₂ (1.10g, 1.50mmol) and KOAc (27.48g, 280.00mmol), 600mL of DMF was added to stir the mixture, and the reaction mixture was heated under reflux for 3 hours. After the reaction is finished, cooling to room temperature, adding distilled water, extracting with dichloromethane, washing an organic phase with distilled water for three times, standing, separating liquid, collecting the organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling, crystallizing, filtering, and recrystallizing the obtained solid with toluene to obtain an intermediate M-2-6 (27.78 g, yield 83%); HPLC purity is more than or equal to 98.72 percent. Mass spectrum m/z:223.1666 (theoretical value: 223.1682).

Preparation of intermediate b-2-6:

under the protection of nitrogen, M-2-6 (26.77g, 120mmol) and M are added into a reaction bottle in sequence ₂ -2-6 (40.82g, 132mmol), potassium carbonate (30.41g, 220m)mol)、Pd(PPh ₃ ) ₄ (1.39g, 1.20mmol), 500mL of a toluene/ethanol/water (3. After the reaction is finished, cooling to room temperature, adding methylbenzene to separate phases, washing the methylbenzene phase with distilled water for three times, standing and separating, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling and crystallizing, filtering, and recrystallizing the obtained solid with toluene to obtain an intermediate b-2-6 (31.96 g, yield 78%). The HPLC purity is more than or equal to 99.71 percent. Mass spectrum m/z:341.2066 (theoretical value: 341.2082).

Preparation of intermediate I-2-6:

under the protection of nitrogen, a-2-6 (25.70g, 80mmol), b-2-6 (27.32g, 80mmol), sodium tert-butoxide (15.38g, 160mmol), pd (dppf) Cl were added to a reaction flask in sequence ₂ (0.59g, 0.8mmol), and 400ml of toluene was added thereto and dissolved, followed by heating and refluxing for 4.5 hours. After the reaction is finished, cooling to room temperature, adding distilled water, extracting with dichloromethane, washing the organic phase with distilled water for three times, standing, separating, collecting the organic phase, drying with anhydrous magnesium sulfate, filtering, distilling and concentrating the filtrate under reduced pressure, cooling, crystallizing, filtering, recrystallizing the obtained solid with ethyl acetate to obtain an intermediate I-2-6 (34.85 g, the yield is 77%), and the purity of the solid is not less than 99.55% through HPLC (high performance liquid chromatography) detection. Mass spectrum m/z:565.2720 (theoretical value: 565.2708).

Preparation of Compounds 2-6:

under the protection of nitrogen, the intermediate I-2-6 (22.63g, 40mmol), c-2-6 (15.89g, 40mmol) and Pd were sequentially added into a reaction flask ₂ (dba) ₃ (0.37g, 0.40mmol), BINAP (0.50g, 0.80mmol) and sodium tert-butoxide (6.73g, 70mmol), 300mL of toluene is added, the mixture is stirred and dissolved, heated and refluxed for 24 hours, after the reaction is finished, the mixture is cooled to room temperature, distilled water is added, dichloromethane is used for extraction, the organic phase is washed with distilled water for three times, the mixture is kept still and separated, the organic phase is collected and dried with anhydrous magnesium sulfate, filtered, the filtrate is concentrated by reduced pressure distillation, cooled and crystallized, is filtered, the obtained solid is recrystallized by toluene, and the compound 2-6 (26.46 g, the yield is 75 percent) is obtained, and the purity of the solid is not less than 99.92 percent by HPLC. Mass spectrum m/z:881.3949 (theoretical value: 881.3960). Theoretical element content (%) C ₆₈ H ₄₃ D ₄ N: c,92.59; h,5.83; n,1.59. Measured elemental content (%): c,92.61; h,5.79; n,1.62.

Synthetic example 12: preparation of Compounds 2-31

According to the preparation method of synthetic example 11, equimolar a-2-6, equimolar b-2-6 and equimolar c-2-6 were replaced with equimolar a-2-31, equimolar b-2-31 and equimolar c-2-31, respectively, to obtain compound 2-31 (26.82 g), which had an HPLC purity of 99.91% or higher. Mass spectrum m/z:881.3975 (theoretical value: 881.3960). Theoretical element content (%) C ₆₈ H ₄₃ D ₄ N: c,92.59; h,5.83; n,1.59. Measured elemental content (%): c,92.62; h,5.79; n,1.61.

Synthetic example 13: preparation of Compounds 2-44

According to the preparation method of synthetic example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of c-2-31, b-2-44 and c-2-31, respectively, to obtain compound 2-44 (25.55 g) with an HPLC purity of 99.95% or more. Mass spectrum m/z:862.4254 (theoretical value: 862.4242). Theoretical element content (%) C ₆₆ H ₃₄ D ₁₁ N: c,91.84; h,6.54; n,1.62. Measured elemental content (%): c,91.79; h,6.56; n,1.59.

Synthesis example 14: preparation of Compounds 2-69

According to the preparation method of synthetic example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of a-2-69, b-2-69 and c-2-69, respectively, to obtain compound 2-69 (21.24 g) with an HPLC purity of 99.93% or more. Mass spectrum m/z:680.3223 (theoretical value: 680.3240). Theoretical element content (%)C ₅₂ H ₃₂ D ₅ N: c,91.73; h,6.22; and N,2.06. Measured elemental content (%): c,91.69; h,6.08; and N,2.10.

Synthetic example 15: preparation of Compounds 2 to 80

According to the preparation method of synthetic example 11, equimolar a-2-6, b-2-6 and c-2-6 were replaced with equimolar a-2-69, b-2-80 and c-2-69, respectively, to obtain compound 2-80 (21.05 g) with an HPLC purity of ≧ 99.97%. Mass spectrum m/z:720.3570 (theoretical value: 720.3553). Theoretical element content (%) C ₅₅ H ₃₆ D ₅ N: c,91.63; h,6.43; n,1.94. Measured elemental content (%): c,91.59; h,6.38; n,1.97.

Synthetic example 16: preparation of Compounds 2-107

According to the preparation method of synthetic example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of c-2-69, b-2-107 and c-2-107, respectively, to obtain compound 2-107 (26.76 g) with an HPLC purity of 99.93% or higher. Mass spectrum m/z:928.4851 (theoretical value: 928.4836). Theoretical element content (%) C ₇₁ H ₅₆ D ₃ N: c,91.77; h,6.72; n,1.51. Measured elemental content (%): c,91.80; h,6.68; and N,1.47.

Synthetic example 17: preparation of Compounds 2 to 123

According to the preparation method of synthetic example 11, equimolar a-2-6, b-2-6 and c-2-6 were replaced with equimolar a-2-123, b-2-123 and c-2-123, respectively, to obtain compound 2-123 (25.73 g) with an HPLC purity of 99.96% or more. Mass spectrum m/z:868.4821 (theoretical value: 868.4805). Theory of the inventionElement content (%) C ₆₆ H ₅₂ D ₅ N: c,91.20; h,7.19; n,1.61. Measured elemental content (%): c,91.18; h,7.21; n,1.57.

Synthetic example 18: preparation of Compounds 2-167

According to the preparation method of synthetic example 11, equimolar a-2-6 and equimolar b-2-6 were replaced with equimolar a-2-69 and equimolar b-2-167, respectively, to obtain compound 2-167 (20.96 g), which had an HPLC purity of ≧ 99.92%. Mass spectrum m/z:737.3946 (theoretical value: 737.3960). Theoretical element content (%) C ₅₆ H ₄₃ D ₄ N: c,91.14; h,6.96; and N,1.90. Measured elemental content (%): c,91.11; h,6.93; n,1.88.

Synthetic example 19: preparation of Compounds 2-183

According to the production method of Synthesis example 11, equimolar a-2-6 and equimolar b-2-6 were replaced with equimolar a-2-183 and equimolar b-2-183, respectively, to give compound 2-183 (22.85 g) having an HPLC purity of not less than 99.94%. Mass spectrum m/z:815.4410 (theoretical value: 815.4429). Theoretical element content (%) C ₆₂ H ₄₉ D ₄ N: c,91.24; h,7.04; n,1.72. Measured elemental content (%): c,91.19; h,7.07; n,1.68.

Synthesis example 20: preparation of Compounds 2-201

According to the production method of synthetic example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of a-2-201, b-2-201 and c-2-201, respectively, to obtain compound 2-201 (21.81 g) with an HPLC purity of 99.91% or more. Mass spectrum m/z:789.4231 (theoretical value: 789.4211). Theoretical element content (%)C ₆₀ H ₃₉ D ₈ N: c,91.21; h,7.01; n,1.77. Measured elemental content (%): c,91.18; h,7.04; n,1.69.

Synthetic example 21: preparation of Compounds 2-245

According to the preparation method of Synthesis example 11, equimolar of a-2-6, b-2-6 and c-2-6 were each replaced with equimolar of n ₃ 2-201, b-2-245 and c-2-245 to obtain compound 2-245 (18.24 g), with HPLC purity ≧ 99.93%. Mass spectrum m/z:690.4009 (theoretical value: 690.4022). Theoretical element content (%) C ₅₂ H ₄₂ D ₅ N: c,90.39; h,7.58; and N,2.03. Measured elemental content (%): c,90.42; h,7.61; and N,2.06.

Synthetic example 22: preparation of Compounds 2-276

According to the preparation method of synthetic example 11, equimolar a-2-6, b-2-6 and c-2-6 were replaced with equimolar a-2-276, b-2-276 and c-2-276, respectively, to obtain compound 2-276 (17.93 g) with an HPLC purity of 99.98% or higher. Mass spectrum m/z:574.3378 (theoretical value: 574.3396). Theoretical element content (%) C ₄₃ H ₃₄ D ₅ N: c,89.85; h,7.71; n,2.44. Measured elemental content (%): c,89.88; h,7.67; and N,2.39.

Synthetic example 23: preparation of Compounds 2-289

According to the preparation method of synthetic example 11, equimolar a-2-6, b-2-6 and c-2-6 were replaced with equimolar a-2-289, b-2-289 and c-2-289, respectively, to obtain compound 2-289 (23.93 g) with an HPLC purity of 99.94% or more. Mass spectrum m/z:866.4633 (theoretical value:866.4648). Theoretical element content (%) C ₆₆ H ₅₀ D ₅ N: c,91.41; h,6.97; n,1.62. Measured elemental content (%): c,91.39; h,6.94; n,1.58.

Synthetic example 24: preparation of Compounds 2-300

According to the preparation method of synthetic example 11, equimolar a-2-6, b-2-6 and c-2-6 were replaced with equimolar a-2-300, b-2-300 and c-2-300, respectively, to obtain compound 2-300 (20.65 g) with HPLC purity ≧ 99.96%. Mass spectrum m/z:758.4634 (theoretical value: 758.4617). Theoretical element content (%) C ₅₇ H ₄₆ D ₇ N: c,90.19; h,7.97; n,1.85. Measured elemental content (%): c,90.21; h,7.95; and N,1.90.

Synthetic example 25: preparation of Compounds 2 to 308

According to the production process of synthetic example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of a-2-308, b-2-308 and c-2-276, respectively, to obtain compound 2-308 (22.58 g) with an HPLC purity of 99.90% or more. Mass spectrum m/z:817.4505 (theoretical value: 817.4524). Theoretical element content (%) C ₆₂ H ₄₃ D ₈ N: c,91.02; h,7.27; n,1.71. Measured elemental content (%): c,91.05; h,7.30; n,1.68.

Synthetic example 26: preparation of Compounds 2-337

According to the preparation method of synthetic example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of a-2-69, b-2-337 and c-2-6, respectively, to obtain compound 2-337 (24.31 g) with an HPLC purity of 99.94% or more. Mass spectrum m/z:843.3821 (theoretical value: 843.3803). Theoretical element content (%) C ₆₅ H ₄₁ D ₄ N: c,92.49; h,5.85; n,1.66. Measured elemental content (%): c,92.52; h,5.88; n,1.64.

Synthetic example 27: preparation of Compounds 2-346

According to the production method of synthetic example 11, equimolar amounts of a-2-6 and b-2-6 were replaced with equimolar amounts of a-2-123 and b-2-346, respectively, to give compound 2-346 (27.64 g), HPLC purity ≧ 99.96%. Mass spectrum m/z:920.5038 (theoretical value: 920.5056). Theoretical element content (%) C ₇₀ H ₄₈ D ₉ N: c,91.26; h,7.22; n,1.52. Measured elemental content (%): c,91.29; h,7.19; n,1.48.

Synthetic example 28: preparation of Compounds 2-377

According to the production method of Synthesis example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of c-2-123, b-2-377 and c-2-123, respectively, to obtain Compound 2-377 (29.21 g) with an HPLC purity of 99.93% or more. Mass spectrum m/z:1122.6853 (theoretical value: 1122.6870). Theoretical element content (%) C ₈₅ H ₈₂ D ₃ N: c,90.86; h,7.89; and N,1.25. Measured elemental content (%): c,90.90; h,7.92; n,1.22.

Synthetic example 29: preparation of Compounds 2-384

According to the preparation method of synthetic example 11, equimolar a-2-6, b-2-6 and c-2-6 were replaced with equimolar c-2-123, b-2-384 and c-2-276, respectively, to obtain compound 2-384 (24.11 g) with an HPLC purity of 99.92% or higher. Mass spectrum m-z:860.5074 (theoretical value: 860.5087). Theoretical element content (%) C ₆₅ H ₅₂ D ₇ N: c,90.65; h,7.72; n,1.63. Measured elemental content (%): c,90.68; h,7.68; n,1.59.

Synthetic example 30: preparation of Compound 2-395

According to the production method of Synthesis example 11, equimolar a-2-6, b-2-6 and c-2-6 were replaced with equimolar a-2-395, b-2-395 and c-2-289, respectively, to give compound 2-395 (23.51 g) with HPLC purity ≧ 99.96%. Mass spectrum m/z:863.4446 (theoretical value: 863.4429). Theoretical element content (%) C ₆₆ H ₄₉ D ₄ N: c,91.73; h,6.65; n,1.62. Measured elemental content (%): c,91.69; h,6.67; n,1.58.

Synthetic example 31: preparation of Compounds 2 to 399

According to the production method of synthetic example 11, equimolar amounts of a-2-6, b-2-6 and c-2-6 were replaced with equimolar amounts of a-2-399, b-2-399 and c-2-69, respectively, to give compound 2-399 (24.05 g) having an HPLC purity of 99.94% or more. Mass spectrum m/z:896.4979 (theoretical value: 896.4994). Theoretical element content (%) C ₆₈ H ₄₀ D ₁₃ N: c,91.03; h,7.41; n,1.56. Measured elemental content (%): c,91.06; h,7.38; and N,1.60.

The energy level was measured using cyclic voltammetry in which the energy level was determined from the relative potential value of the electrode potential value with respect to a known reference potential, and table 1 is the HOMO level test result of the compound prepared in the example of the present invention.

TABLE 1 HOMO energy levels of the compounds prepared in the examples of the present invention

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As can be seen from Table 1, the HOMO energy level of the hole transport layer material is between-5.02 eV and-5.19 eV, the HOMO energy level of the electron blocking layer material is between-5.23 eV and-5.29 eV, the absolute value of the difference between the HOMO value of the hole transport layer material and the HOMO value of the electron blocking layer material is more than or equal to 0eV and less than or equal to 0.25eV, and the energy level relationship can solve the problem of accumulation of holes between the electron blocking layer and the light emitting layer.

Device examples 1 to 24

The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropyl acetone for 20 min, and drying at 120 deg.C. Vacuum evaporating HI on the ITO substrate to form an evaporated layer with the thickness of 15nm as a hole injection layer; vacuum evaporating the compound 1-3 of the invention on the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 80nm; vacuum evaporating the compound 2-384 as an electron blocking layer on the hole transport layer, wherein the evaporation thickness is 40nm; vacuum evaporation is carried out on the electron blocking layer, wherein BH-1 BD-1=96 (mass ratio) is used as a light emitting layer, and the evaporation thickness is 20nm; HB is evaporated on the luminescent layer in vacuum to be used as a hole blocking layer, and the evaporation thickness is 15nm; performing vacuum evaporation on the hole blocking layer to form ET as an electron transport layer, wherein the evaporation thickness is 30nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70nm.

Device examples 2 to 24: the compounds 1 to 8,1 to 25, 1 to 36, 1 to 44, 1 to 61, 1 to 75, 1 to 107, 1 to 181, 1 to 191, 1 to 237, 1 to 253, 1 to 287, 1 to 319, 1 to 322, 1 to 336, 1 to 356, 1 to 370, 1 to 405, 1 to 470, 1 to 523, 1 to 555, 1 to 676, 1 to 757 according to the present invention were used as hole transport layer materials in place of the compounds 1 to 3 according to the present invention in device example 1, and the compounds 2 to 346, 2 to 300, 2 to 69, 2 to 80, 2 to 245, 2 to 337, 2 to 377, 2 to 183, 2 to 31, 2 to 308, 2 to 300, 2 to 395, 2 to 384, 2 to 399, 2 to 6, 2 to 167, 2 to 201, 2 to 123, 2 to 44, 2 to 245, 2 to 276, 2 to 384 and 2 to 107 according to the present invention in example 1 were used as hole transport layer materials in the same manner as in the organic light emitting device example 1 except that the organic light emitting layer materials were used in the same manner as in the organic light emitting layer material in the organic light emitting device example 1.

Comparative examples 1 to 20: an organic electroluminescent device was produced by using the same procedure as in device example 1 except that compounds 1 to 61, compounds 1 to 370, compounds 1 to 555, compounds 1 to 676, comparative compound 1, comparative compound 2, comparative compound 3, compounds 1 to 181, compounds 1 to 319, compounds 1 to 370, compounds 1 to 405, compounds 1 to 470 and NPB were used as hole transport layer materials, respectively, instead of compounds 1 to 3 of the present invention in device example 1, and compounds 4, comparative compound 5, compounds 2 to 69, compounds 2 to 167, compounds 2 to 107, compounds 2 to 123, compounds 2 to 183, compounds 2 to 399, TPD, compounds 2 to 123, compounds 2 to 167, compounds 2 to 183, compounds 2 to 201 and compounds 2 to 289 were used as electron blocking layer materials, respectively, instead of compounds 2 to 384 of the present invention in device example 1.

Comparative example 21: the ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropyl acetone for 20 min, and drying at 120 deg.C. Vacuum evaporating HI on the ITO substrate to form an evaporated layer with the thickness of 15nm as a hole injection layer; vacuum evaporating the compounds 1-8 of the invention on the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 120nm; vacuum evaporation of BH-1 BD-1=96 (mass ratio) on the hole transport layer to serve as a light emitting layer, wherein the evaporation thickness is 20nm; HB is evaporated on the luminescent layer in vacuum to be used as a hole blocking layer, and the evaporation thickness is 15nm; performing vacuum evaporation on the hole blocking layer to form an ET (electron transport layer) with the evaporation thickness of 30nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70nm.

Comparative examples 22, 23: organic electroluminescent devices were produced by using the same procedures as in comparative example 21, except that the compounds 1 to 181 and 1 to 322 according to the invention were used as hole transport layer materials, respectively, instead of the compounds 1 to 8 according to the invention in comparative example 19.

The test software, computer, K2400 digital source manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a joint IVL test system to test the luminous efficiency of the organic electroluminescent device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment for testing is atmospheric environment, and the temperature is room temperature.

The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 2. Table 2 shows the results of the test of the light emitting characteristics of the organic electroluminescent devices prepared by the compounds prepared in the inventive examples and the comparative materials.

Table 2 luminescence characteristic test of light emitting device

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It can be seen from table 2 that the energy level relationship of the organic electroluminescent device of the present invention not only helps to effectively confine the holes in the light emitting layer to be combined with the electrons to form exciton luminescence, but also the exciton recombination region moves to the center of the light emitting layer, so that the accumulation of the holes at the interface between the light emitting layer and the electron blocking layer is effectively avoided, thereby improving the efficiency and lifetime of the organic electroluminescent device.

It is to be understood that the present invention has been particularly shown and described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the spirit and scope of the invention.

Claims

1. An organic electroluminescent device, comprising: an anode and a cathode which are oppositely arranged, a light-emitting layer between the anode and the cathode, an electron-blocking layer between the light-emitting layer and the anode, and a hole-transporting layer between the electron-blocking layer and the anode, characterized in that the HOMO level of the electron-blocking layer is equal to or less than the HOMO level of the hole-transporting layer, and the absolute value of the difference between the HOMO value of the hole-transporting layer and the HOMO value of the electron-blocking layer is greater than or equal to 0.03eV and less than or equal to 0.24eV,

the material of the hole transport layer is selected from the structure shown in the following formula 1,

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the R is ₁ 、R ₅ 、R ₇ Any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl and phenyl which are the same or different; the R is ₁ May be substituted with one or more substituents selected from methyl; said R is ₅ May be substituted by one or more substituents selected from methyl; the R is ₇ May be substituted with one or more substituents selected from methyl;

a is a ₁ The same or different is selected from 0,1, 2,3, 4 or5; a is a ₂ The same or different is selected from 0,1, 2 or 3; a is a ₃ The same or different is selected from 0,1, 2,3 or 4; a is a ₅ The same or different is selected from 0,1, 2,3, 4,5 or 6; a is a ₆ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; when two or more R's are present ₁ When two or more R are present ₁ Are the same or different from each other; when two or more R's are present ₅ When two or more R are present ₅ Are the same or different from each other;

q is a number of ₁ The same or different is selected from 0,1, 2,3, 4 or 5; q is a number of ₂ Identical or different from 0,1, 2,3 or 4; q is a number of ₃ Identical or different from 0,1, 2,3, 4,5, 6,7 or 8; q is a number of ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; q is a radical of ₅ Identical or different from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; q is a number of ₆ The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; q is a radical of ₇ The same or different is selected from 0,1, 2,3, 4,5 or 6; when two or more R's are present ₇ When two or more R are present ₇ The same or different from each other;

the above-mentioned

Any one selected from the structures shown below,

the R is ₀ Any one selected from deuterium, methyl, ethyl, isobutyl, tert-butyl and phenyl; the R is ₀ May be substituted with one or more substituents selected from deuterium;

the R is ₆ Any one selected from deuterium and methyl; the R is ₆ May be substituted with one or more substituents selected from deuterium;

n is ₃ Is selected from 1,2, 3 or 4, and R ₀ At least one of which is chosen from deuterium; n is said _3-1 Selected from 0,1, 2,3 or 4;

n is ₄ The same or different is selected from 0,1 or 2; b is ₂ The same or different is selected from 0,1, 2,3 or 4; b is ₃ The same or different is selected from 0,1, 2,3, 4,5 or 6; b is ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; b is described ₅ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; b is described ₆ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; with the proviso that when- (R) ₀ )n ₄ When not deuterium, - (R) ₆ )b ₂ At least two of which are deuterium, - (R) ₆ )b ₃ At least two of which are deuterium, - (R) ₆ )b ₄ At least two of which are deuterium, - (R) ₆ )b ₅ At least two of which are deuterium, - (R) ₆ )b ₆ At least two of which are deuterium;

the above-mentioned

Selected from any one of the structures shown below,

the Ra, rb and R ₈ Any one of hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, norbornyl and phenyl, which are the same or different; the Ra may be substituted with one or more substituents selected from deuterium; said Rb may be substituted with one or more substituents selected from deuterium; the R is ₈ May be substituted with one or more substituents selected from deuterium;

m is said ₂ Selected from 0,1, 2 or 3; when two or more Rb are present, the two or more Rb may be the same or different from each other, or two adjacent Rb may be linked to each other to form a substituted or unsubstituted benzene ring;

said p is ₁ Identical or different from 0,1, 2,3 or 4; said p is ₆ The same or different is selected from 0,1, 2,3, 4 or 5; said p is ₇ Identical or different from 0,1, 2,3, 4,5, 6 or 7; said p is ₈ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8 or 9; said p is ₉ The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10 or 11; said p is ₁₀ Identical or different from 0,1, 2 or 3; when two or more R's are present ₈ When two or more R are present ₈ Are the same or different from each other;

said L ₁ 、L ₂ The same or different is selected from a single bond or any one of the structures shown below,

said R is ₉ The same or different is selected from any one of hydrogen, methyl, ethyl, isopropyl and tert-butyl;

v is ₁ The same or different is selected from 0,1, 2,3 or 4; v is ₂ Identical or different from 0,1, 2,3, 4,5, 6 or 7; when two or more R's are present ₉ When two or more R are present ₉ The same or different from each other.

2. The organic electroluminescent device according to claim 1, wherein the formula 1 is selected from any one of the following structures,

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3. the organic electroluminescent device as claimed in claim 1, wherein the electron blocking layer is made of a material selected from the group consisting of the following structures represented by formula 2,

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in the formula (2), the reaction mixture is,

ar is _a 、Ar _b The same or different is selected from any one of the structures shown below,

said R is _c 、R _d 、R _i The same or different is selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl and tert-butyl;

m is said _a Identical or different from 0,1, 2 or 3; m is said _b Identical or different from 0,1, 2,3 or 4; m is said _c Identical or different from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; m is said _d The same or different is selected from 0,1, 2,3, 4,5 or 6; m is said _e Identical or different from 0,1, 2,3, 4,5, 6,7 or 8; m is said _f The same or different is selected from 0,1, 2,3, 4,5, 6,7,8 or 9; m is said _g The same or different is selected from 0,1, 2,3, 4 or 5; when two or more R's are present _c When two or more R are present _c Are the same or different from each other; when two or more R's are present _d When two or more R are present _d Are the same or different from each other;

v is _a Identical or different from 0,1, 2,3, 4,5, 6,7 or 8; v is _b The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; v is _c The same or different is selected from 0,1, 2,3, 4 or 5; v is _d The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10 or 11; v is _e The same or different is selected from 0,1, 2,3, 4,5, 6,7,8 or 9; v is _f Identical or different from 0,1, 2,3 or 4; v is _g The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; v is _i The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11 or 12; when two or more R's are present _i When two or more R are present _i The same or different from each other;

ar is _c Any one selected from the structures shown below,

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said R is _h The same or different is selected from any one of hydrogen, deuterium, methyl, isopropyl and tert-butyl;

the R is _h May be substituted with one or more substituents selected from deuterium;

n is _a The same or different is selected from 0,1, 2,3, 4 or 5; n is _b The same or different is selected from 0,1, 2 or 3; n is _c The same or different is selected from 0,1, 2 or 3; n is _d The same or different is selected from 0,1 or 2; n is _e The same or different is selected from 0,1, 2,3, 4,5 or 6; n is _f The same or different is selected from 0,1, 2,3, 4,5, 67 or 8; n is _g The same or different is selected from 0,1, 2,3, 4,5, 6,7,8, 9 or 10; when two or more R's are present _h When two or more R are present _h Are the same or different from each other;

said L _a ～L _c The same or different is selected from a single bond or any one of the structures shown below,

the R is _k The same or different is selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl and tert-butyl;

k is the same as ₁ The same or different is selected from 0,1, 2,3 or 4; when two or more R's are present _k When two or more R are present _k Are the same or different from each other, or two adjacent R _k Are linked to each other to form substituted or unsubstituted: cyclopentene, cyclohexene, cyclopentane, cyclohexane, said "substituted or unsubstituted" meaning unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium;

the above-mentioned

Containing at least one deuterium. />