CN115802781B

CN115802781B - Organic electroluminescent device

Info

Publication number: CN115802781B
Application number: CN202310015462.XA
Authority: CN
Inventors: 郭建华; 杜明珠; 孙月; 刘小婷
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-01-05
Filing date: 2023-01-05
Publication date: 2024-08-13
Anticipated expiration: 2043-01-05
Also published as: CN115802781A

Abstract

The invention provides an organic electroluminescent device, and belongs to the technical field of organic electroluminescence. According to the organic electroluminescent device provided by the invention, the carbazole derivative and the heterocyclic derivative are introduced into the luminescent layer main material, so that the carbazole derivative and the heterocyclic derivative have similar physical properties and good carrier transmission characteristics, and when the carbazole derivative and the heterocyclic derivative are used as the luminescent layer main material together, the luminescent efficiency of the organic electroluminescent device can be greatly improved, and the service life of the organic electroluminescent device can be prolonged. 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

As a new generation of mainstream display technology, an organic light-EmittingDiode, OLED has the advantages of high efficiency, good flexibility, wide viewing angle, high brightness, high contrast, high color gamut, high resolution, low energy consumption, low driving voltage, high response speed and the like, and as the OLED technology is increasingly perfect and the cost is gradually reduced, the market demand of the OLED is accelerated to increase the period, and the organic light-emitting diode is widely applied to various fields such as display and illumination, and is one of the most promising new display technologies, and is one of the competitive hot spots in the international high-tech field.

The OLED includes an anode, a cathode, and an organic layer including 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, a capping layer, and the like. The OLED is a dual injection type light emitting device, electrons injected from a cathode and holes injected from an anode are combined in a light emitting layer to form excitons under the driving of external voltage, and the excitons are radiated to be de-excited to emit photons, so that a light emitting phenomenon is generated.

The light-emitting layer is a key to improve the performance of the OLED, and the light-emitting layer generally comprises a host material and a doping material, wherein the host material mainly plays a role in energy transfer, when only a single material is used as a host of the light-emitting layer, the problem of unbalanced carrier transmission exists, and in order to balance carrier transmission, reduce exciton quenching and improve the light-emitting efficiency and service life of the device, a double-host material can be used to replace a single-host material, one of the selected double-host materials needs to be a hole-transmission type host material, and the other is an electron-transmission type host material, but most of the existing double-host collocations cannot enable the electron transmission and the hole transmission in the light-emitting layer to reach a proper balance.

Therefore, in the selection of the dual-host materials, a plurality of elements need to be paid attention to, rather than simply mixing the two materials, not only the energy level matching problem between the host materials of the materials needs to be considered, but also the balance of hole transmission and electron transmission capability needs to be considered, and only the electron transmission and the hole transmission in the light-emitting layer need to reach a proper balance, the maximum recombination of excitons in the light-emitting layer can be realized, so that the light-emitting efficiency and the service life of the device can be effectively improved only through proper material collocation.

Disclosure of Invention

The invention provides an organic electroluminescent device, which solves the problem that the hole and electron of the organic electroluminescent device in the prior art are difficult to balance, so that the device has poor performance, and the device not only has higher luminous efficiency, but also has longer service life.

The invention provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a luminescent layer, the luminescent layer comprises a main body material and a doping material, the main body material comprises carbazole derivatives shown in a formula 1 and heterocyclic derivatives shown in a formula 2,

In the formula 1, the L ₁ is selected from any one of the structures shown in the following,

The R ₅ is the same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C30 aryl;

The f ₁ are the same or different and are selected from 0, 1,2, 3 or 4; when two or more R ₅ are present, two or more R ₅ are the same or different from each other, or adjacent R ₅ are linked to each other to form a substituted or unsubstituted alicyclic ring;

Ar ₁ is selected from any one of substituted or unsubstituted C3-C12 alicyclic group and substituted or unsubstituted C6-C30 aryl;

The L ₂、L₃ is the same or different and is selected from any one of single bond, substituted or unsubstituted C3-C12 alicyclic group and substituted or unsubstituted C6-C30 arylene group;

the R ₁ is the same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C30 aryl;

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

The R ₂、R₃ is the same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C18 aryl;

The b and the c are the same or different and are selected from 0,1, 2, 3 or 4; when two or more R ₂ are present, two or more R ₂ are the same or different from each other, or adjacent R ₂ are linked to each other to form a substituted or unsubstituted ring; when two or more R ₃ are present, two or more R ₃ are the same or different from each other, or adjacent R ₃ are linked to each other to form a substituted or unsubstituted ring;

in the formula 2, A is selected from any one of the structures shown below,

The z is the same or different and is selected from CRa or N;

Y ₁、Y₂ is the same or different and is selected from any one of CRzRy, NRx, O, S;

The Rz, ry and Rx are the same or different and are selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C18 aryl;

the Ra is the same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C18 aryl; when two or more Ra are present, two or more Ra are the same or different from each other, or adjacent Ra are linked to each other to form a substituted or unsubstituted ring;

The R ₆、R₇、R₈ is the same or different and is selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl and substituted or unsubstituted quinazolinyl; the R ₆、R₇ groups may be linked to form a substituted or unsubstituted ring;

The La is selected from any one of single bond, substituted or unsubstituted C3-C12 alicyclic group and substituted or unsubstituted C6-C30 arylene group;

The L ₄ is selected from any one of the structures shown below,

Wherein at least one R ₉ is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C30 alkenyl, or two adjacent R ₉ can be connected with each other to form a substituted or unsubstituted alicyclic ring, and the rest R ₉ is the same or different and is selected from any one of hydrogen, deuterium, halogen and cyano;

The e ₁ are the same or different and are selected from 0,1,2, 3 or 4; the e ₂ are the same or different and are selected from 0,1,2, 3, 4, 5 or 6; when two or more R ₉ are present, two or more R ₉ are the same or different from each other;

the X ₁ is any one selected from O, S, NRb;

the Rb is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C18 aryl;

the x is the same or different and is selected from CRc or N;

The Rc and R ₄ are the same or different and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C18 aryl.

The invention has the beneficial effects that:

According to the organic electroluminescent device provided by the invention, the main material in the luminescent layer comprises the carbazole derivative shown in the formula 1 and the heterocyclic derivative shown in the formula 2, the carbazole derivative shown in the formula 1 has a relatively wide energy gap, the heterocyclic derivative shown in the formula 2 has a relatively narrow energy gap, the hole transmission and the electron transmission in the luminescent layer reach proper balance under the combined action of the carbazole derivative and the heterocyclic derivative, so that the recombination probability of excitons in the luminescent layer is maximized, and the carbazole derivative shown in the formula 1 and the heterocyclic derivative shown in the formula 2 have the same or similar molecular weight, so that the carbazole derivative and the heterocyclic derivative have similar physical properties, and can be used as the main material of the luminescent layer in the organic electroluminescent device, so that the luminescent efficiency of the device can be improved, and the service life of the device can be effectively prolonged.

Drawings

Fig. 1 is a cross-sectional view of a structure of an organic electroluminescent device 100 according to an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. And embodiments of the invention and features of the embodiments may be combined with each other without conflict. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.

Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.

In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance.

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

In this specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example, the number of the cells to be processed,Can representAnd so on.

In this specification, when a substituent or linkage site is located across two or more rings, it is meant that it may be attached to either of the two or two rings, in particular to either of the respective selectable sites of the rings. For example, the number of the cells to be processed,Can representOr (b)Can representCan representOr (b) Can representAnd so on.

Halogen refers to fluorine, chlorine, bromine and iodine;

The alkyl group according to the present invention means a monovalent group obtained by removing 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, particularly preferably 1 to 6 carbon atoms, and examples may include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, etc., but are not limited thereto.

The alicyclic ring of the present invention means a cyclic hydrocarbon having an aliphatic nature, which contains a closed carbocyclic ring in the molecule, and may be a cycloalkane, cycloalkene, etc., preferably has 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, most preferably 3 to 7 carbon atoms, and examples may include, but are not limited to, cyclopropane, cyclobutane, cyclopentene, cyclohexacarbon, cycloheptane, adamantane, norbornane, cyclopropene, cyclobutene, cyclopentene, cyclohexaalkene, cycloheptene, etc.

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

The aryl group according to the present invention means a monovalent group obtained by removing one hydrogen atom from the aromatic nucleus 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 phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, indenyl, indanyl, dihydronaphthyl, tetrahydronaphthyl, anthracenyl, phenanthryl, pyrenyl, triphenylenyl, perylenyl, and the like, but are not limited thereto.

The arylene group refers to a bivalent group formed by removing two hydrogen atoms from the aromatic nucleus carbon of an aromatic hydrocarbon molecule. These are not only divalent groups but also aryl groups as described above.

The alicyclic group refers to a divalent group formed by removing two hydrogen atoms from an alicyclic hydrocarbon molecule. These are not only divalent groups but also alicyclic groups as described above.

Heteroaryl as used herein refers to the generic term for a monovalent radical that is formed by removing a hydrogen atom from the core atom of an aromatic heterocycle comprising carbon and a heteroatom. The heteroatom may be one or more of N, O, S, si, P, and may be a monocyclic heteroaryl group or a condensed ring 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, quinolinyl, isoquinolinyl, oxazolyl, thiazolyl, imidazolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, pyridooxazolyl, pyridothiazolyl, pyridoimidazolyl, pyrimidothiazolyl, dibenzofuranyl, dibenzothienyl, quinoxalinyl, quinazolinyl, quinoxazolyl, quinolizinyl, quinoimidazoimidazolyl, purinyl, 2-purinyl, N-imidazolyl, and the like, but are not limited thereto.

The heteroarylene group according to the present invention is a divalent group obtained by removing two hydrogen atoms from a core atom of an aromatic heterocycle composed of carbon and a heteroatom. They may be applied to the above description of heteroaryl groups, in addition to the divalent groups, respectively.

"Alkoxy" as used herein is a monovalent group consisting of an alkyl group and an oxygen atom, preferably having 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms, and examples may include methoxy, ethoxy, propoxy, and the like, but are not limited thereto.

"Substituted" as used 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.

"Substituted or unsubstituted" as used herein means unsubstituted 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 group, substituted or unsubstituted C1-C25 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C30 alicyclic group and C6-C30 aromatic ring fused ring group, substituted or unsubstituted C1-C25 heterocycloalkyl group 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, preferably protium, deuterium, tritium, halogen atom, cyano, C1-C12 alkyl, C3-C18 alicyclic, C6-C25 aryl, C2-C25 heteroaryl, specific examples may include protium, deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, cyclopentenyl, cyclohexenyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocyclopentenyl, benzocyclohexenyl, phenyl, tolyl, mesityl, pentadeutero-phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, benzophenanthryl, pyrenyl, triphenylenyl,A group, perylene group, fluoranthenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, carbazolyl group, 9-phenylcarbazolyl group, spirobifluorenyl group, carbazoloindolyl group, pyrrolyl group, furanyl group, thienyl group, indolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, oxazolyl group, thiazolyl group, imidazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, benzimidazolyl group, pyridooxazolyl group, pyridothiazolyl group, pyridoimidazolyl group, pyrimidothiazolyl group, pyrimidoimidazolyl group, quinolino oxazolyl group, quinophthiazolyl group, phenothiazinyl group, phenoxazinyl group, acridinyl group, 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 two or more substituents are the same or different from each other.

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

in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed 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 term "attached to form a substituted or unsubstituted alicyclic ring" as used herein means that two groups are attached to each other by a chemical bond to form an alicyclic ring, as exemplified below:

In the present invention, examples of the alicyclic ring formed by the connection may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, cycloheptene, but are not limited thereto.

Embodiments of the organic electroluminescent device according to the present invention will be described below with reference to the drawings, but the embodiments of the present invention may be modified into other forms, and the scope of the present invention is not limited to the embodiments described below.

In describing the structural elements of the present invention, the use of the terms "comprising" or "comprises" and the like in the present invention means that the device or article preceding the term encompasses the device or article listed after the term and equivalents thereof without excluding other devices or articles. The terms "connected" or "connected," and the like, are not limited 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, which may also be changed when the absolute positions of the structural elements being described are changed. In the case where a structural element such as a layer, a film, a region, or a plate is located "on" another structural element, it is understood that the structural element is located "directly above" the other structural element, and that the structural element is located in the middle. In contrast, when one structural element is located "directly above" another structural element, it is understood that there are no other structural elements in between.

Fig. 1 is a sectional view schematically showing the structure of an organic electroluminescent device 100 according to an embodiment of the present invention.

Referring to fig. 1, an organic electroluminescent device 100 according to the present invention includes an anode 1, an organic layer 20, and a cathode 2, wherein the organic layer 20 includes a light emitting layer 3, the light emitting layer 3 includes a host material and a doping material, and the host material includes a carbazole derivative represented by formula 1 and a heterocyclic derivative represented by formula 2.

In the organic electroluminescent device 100, the main material in the luminescent layer 3 comprises carbazole derivatives shown in formula 1 and heterocyclic derivatives shown in formula 2, which have similar physical properties, and the carbazole derivatives shown in formula 1 have relatively wide energy gaps and good hole transmission characteristics, the heterocyclic derivatives shown in formula 2 have relatively narrow energy gaps and good electron transmission characteristics, and the good carrier transmission characteristics of the carbazole derivatives and the heterocyclic derivatives can enable carrier transmission in the luminescent layer 3 to reach proper balance, so that the recombination probability of excitons in the luminescent layer 3 is effectively improved, and further the luminous efficiency and the service life of the organic electroluminescent device 100 are improved.

The structure of the organic electroluminescent device 100 including the carbazole-based derivative represented by formula 1 and the heterocyclic-based derivative represented by formula 2 as the host material of the light-emitting layer 3 will be described in more detail below.

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

Anode

In the organic electroluminescent device 100 according to the present invention, the anode 1 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 1 material that can 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.

Organic layer

In the organic electroluminescent device 100 according to the present invention, the organic layer 20 may include one or more kinds selected from the group consisting of the hole transport region 4, the light emitting layer 3, and the electron transport region 5, without limitation, and may have a conventional structure used as an organic layer of an organic electroluminescent device.

Hole transport region

In the organic electroluminescent device 100 according to the present invention, the hole transport region 4 included therein serves to move holes injected from the anode 1 to the light emitting layer 3.

The hole transport region 4 may include an electron blocking layer 6, and at least one of a hole injection layer 8 and a hole transport layer 7.

The hole transport region 4 may have an electron blocking layer 6, a hole injection layer 8, a hole transport layer 7, an electron blocking layer 6 and a hole injection layer 8, a hole transport layer 7 and a hole injection layer 8, an electron blocking layer 6 and a hole transport layer 7, or a structure having an electron blocking layer 6, a hole transport layer 7 and a hole injection layer 8 with the light emitting layer 3 as a reference. Preferably, the hole transport region 4 includes an electron blocking layer 6, a hole transport layer 7, and a hole injection layer 8.

The hole injection layer 8 according to the present invention preferably uses a material having a good hole accepting ability. Specific examples of the material of the hole injection layer 8 that can be used in the present invention may include silver oxide, vanadium oxide, tungsten oxide, copper oxide, metal oxide such as titanium oxide, phthalocyanine compound, biphenylamine compound, phenazine compound, and the like, such as copper phthalocyanine (CuPc), titanyl phthalocyanine, N ' -diphenyl-N, N ' -bis- [4- (N, N-diphenyl amine) phenyl ] benzidine (NPNPB), N ' -tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), and a bisquinoxalino [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-hexaazabenzophenanthrene (HAT-CN), 4',4 "-tris (N, N-diphenylamino) triphenylamine (TDATA), etc., but is not limited thereto.

The hole transport layer 7 according to the present invention preferably uses a material having good hole transport properties. Specific examples of the material of the hole transport layer 7 that can be used in the present invention may include materials such as diphenylamines, triphenylamines, fluorenes, and carbazoles, such as N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-di (naphthalen-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (α -NPD), N' -diphenyl-N, N '-di (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (TPD), 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), 4',4 "-tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but are not limited thereto.

The electron blocking layer 6 according to the present invention preferably uses a material having good electron blocking properties. Specific examples of the electron blocking layer 6 material that can be used in the present invention may include materials such as diphenylamines, triphenylamines, fluorenes, triarylamines, and carbazoles, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (α -NPD), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), and the like, but are not limited thereto.

Light-emitting layer

In the organic electroluminescent device 100 according to the present invention, the light emitting layer 3 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 according to the material constituting the light emitting layer 3. The light emitting layer 3 comprises a host material and a doping material, the mixing ratio of which can be suitably adjusted within the range known in the art, the host material comprises carbazole derivatives represented by formula 1 and heterocyclic derivatives represented by formula 2,

in the formula 2, A is selected from any one of the structures shown below,

The z is the same or different and is selected from CRa or N;

The L ₄ is selected from any one of the structures shown below,

the X ₁ is any one selected from O, S, NRb;

the x is the same or different and is selected from CRc or N;

Preferably, ar ₁ is selected from any one of the structures shown below,

The Rc, rd and Re are the same or different and are selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C18 aryl; the Rc, rd may be joined to form a substituted or unsubstituted ring;

The R ₁₀ is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic and substituted or unsubstituted C6-C18 aryl;

Said g ₁ are the same or different and are selected from 0,1,2,3,4 or 5; said g ₂ are the same or different and are selected from 0,1,2,3 or 4; said g ₃ are the same or different and are selected from 0,1,2,3,4, 5,6 or 7; said g ₄ are the same or different and are selected from 0,1,2,3,4, 5,6,7,8 or 9; said g ₅ are the same or different and are selected from 0,1,2,3,4, 5,6,7,8,9, 10 or 11; said g ₆ are the same or different and are selected from 0,1,2,3,4, 5,6,7 or 8; when two or more R ₁₀ are present, two or more R ₁₀ are the same or different from each other, or adjacent R ₁₀ are linked to each other to form a substituted or unsubstituted ring.

Preferably, the R ₁₀ is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; the R ₁₀ can be substituted by one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; when two or more substituents are present, the two or more substituents may be the same or different from each other, or adjacent R ₁₀ may be linked to each other to form a substituted or unsubstituted ring.

Preferably, L ₂、L₃ is the same or different and is selected from single bond or any one of the structures shown below,

R ₁₁ and Ri are the same or different and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C6-C18 aryl;

The h ₁ are the same or different and are selected from 0, 1,2,3 or 4; the h ₂ are the same or different and are selected from 0, 1,2,3, 4, 5 or 6; the h ₃ are the same or different and are selected from 0, 1,2,3, 4, 5, 6, 7 or 8; the h ₄ are the same or different and are selected from 0, 1,2,3, 4, 5, 6, 7, 8, 9 or 10; the h ₅ are the same or different and are selected from 0, 1,2,3, 4, 5, 6 or 7; when two or more R ₁₁ are present, two or more R ₁₁ are the same or different from each other;

The j ₁ are the same or different and are selected from 0,1,2,3, 4,5 or 6; the j ₂ are the same or different and are selected from 0,1,2,3, 4,5,6, 7 or 8; the j ₃ are the same or different and are selected from 0,1,2,3 or 4; when two or more ris are present, the two or more ris are the same or different from each other.

Preferably, the R ₁₁ is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; the R ₁₁ may be substituted with one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylyl; when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, the Ri is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; the Ri can be substituted by one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylyl; when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, the carbazole derivative represented by formula 1 is selected from any one of the structures shown below,

Preferably, the heterocyclic derivative shown in the formula 2 is selected from any one of the structures shown in the following,

Preferably, A is selected from any one of the structures shown below,

The Ra and the R ₁₂ are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C6-C18 aryl;

The v ₁ are the same or different and are selected from 0, 1,2, 3,4, 5 or 6; the v ₂ are the same or different and are selected from 0, 1,2, 3,4, 5, 6, 7 or 8; the v ₃ are the same or different and are selected from 0, 1,2, 3,4 or 5; when two or more Ra are present, the two or more Ra are the same or different from each other;

The n ₁ are the same or different and are selected from 0, 1,2, 3, 4, 5, 6, 7 or 8; the n ₂ are the same or different and are selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 or 10; the n ₃ are the same or different and are selected from 0, 1,2, 3, 4 or 5; the n ₄ are the same or different and are selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; the n ₅ are the same or different and are selected from 0, 1,2, 3, 4, 5, 6, 7, 8 or 9; the n ₆ are the same or different and are selected from 0, 1,2, 3 or 4; said n ₇ are the same or different and are selected from 0, 1,2, 3, 4, 5, 6 or 7; the n ₈ are the same or different and are selected from 0, 1,2 or 3; the n ₉ are the same or different and are selected from 0, 1,2, 3, 4, 5 or 6; when two or more R ₁₂ are present, the two or more R ₁₂ are the same or different from each other.

Preferably, ra is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene; the Ra can be substituted by one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylenyl; when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, the R ₁₂ is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; the R ₁₂ can be substituted by one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, rz, ry and Rx are the same or different and are selected from any one of methyl, ethyl, isopropyl, tertiary butyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; the Rz may be substituted with one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene; when two or more substituents are present, the two or more substituents may be the same or different from each other. The Ry may be substituted with one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; when two or more substituents are present, the two or more substituents may be the same or different from each other. The Rx may be substituted with one or more substituents which may be the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylyl; when two or more substituents are present, the two or more substituents may be the same or different from each other.

In the present invention, at most one or at most two of the 4 x groups of each ring are selected from N, and the remainder are selected from CRc. More preferably, when there are two x selected from N, the two N are not adjacent.

In the present invention, at most one or at most two of the 4 z groups of each ring are selected from N, and the remainder are selected from CRa. More preferably, when there are two z selected from N, the two N are not adjacent.

Preferably, L ₄ is the same or different and is selected from any one of the structures shown below,

At least one of the R ₉ is selected from any one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, pentyl, ethenyl, propenyl, butenyl, pentenyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, the rest R ₉ being identical or different and selected from any one of hydrogen, deuterium, halogen, cyano; r ₉, in the case of being substituted with two or more substituents, the two or more substituents are the same or different from each other;

The R ₉' is the same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C2-C30 alkenyl;

The R ₁₃ is the same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C2-C30 alkenyl;

The e ₁ are the same or different and are selected from 0,1, 2, 3 or 4; the e ₂ are the same or different and are selected from 0,1, 2, 3, 4,5 or 6; the e ₃ are the same or different and are selected from 0,1 or 2; the e ₄ are the same or different and are selected from 0,1, 2 or 3; when two or more R ₉ are present, two or more R ₉ are the same or different from each other; when two or more R ₉ 'are present, the two or more R ₉' are the same or different from each other;

The p ₁ are the same or different and are selected from 0,1, 2,3, 4, 5, 6, 7 or 8; the p ₂ are the same or different and are selected from 0,1, 2,3, 4, 5 or 6; the p ₃ are the same or different and are selected from 0,1, 2,3 or 4; the p ₄ are the same or different and are selected from 0,1 or 2; the p ₅ are the same or different and are selected from 0,1, 2,3, 4, 5, 6, 7, 8, 9 or 10; when two or more R ₁₃ are present, the two or more R ₁₃ are the same or different from each other.

Preferably, the saidSelected from any one of the structures shown below,

The Rc is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C6-C18 aryl;

The m ₁ are the same or different and are selected from 0, 1, 2, 3 or 4; the m ₂ are the same or different and are selected from 0, 1, 2, 3, 4, 5 or 6; the m ₃ are the same or different and are selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the m ₄ are the same or different and are selected from 0, 1, 2 or 3; the m ₅ are the same or different and are selected from 0, 1, 2, 3, 4 or 5; the m ₆ are the same or different and are selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m ₇ are the same or different and are selected from 0, 1 or 2; when two or more Rc are present, the two or more Rc are the same or different from each other;

the R ₄ is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted C6-C18 aryl.

Preferably, rc is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; the Rc may be substituted with one or more substituents which are the same or different and are selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylyl; when two or more substituents are present, the two or more substituents may be the same or different from each other.

In the light-emitting layer 3 of the present invention, the weight ratio of the carbazole derivative represented by formula 1 to the heterocyclic derivative represented by formula 2 is 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 30:70 to 70:30, more preferably 40:60 to 60:40, and most preferably 50:50.

The doping material included in the light emitting layer 3 according to the present invention may be a doping material known in the art, and specific examples may include complex compounds of transition metals, lanthanoids, actinoids, but are not limited thereto. Preferably, the doping material has a structure represented by the following formula 3:

M is any one selected from Ir, pt, pd, au, rh, ru, os, re, cu, ag, ni, co, W, eu;

the L is selected from formula 3-1 or formula 3-2:

The R ₁₀₀ to R ₁₀₃ are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl and substituted or unsubstituted C1-C30 alkoxy; or R ₁₀₀ to R ₁₀₃ may be linked to adjacent substituents to form a substituted or unsubstituted ring;

the R ₁₀₄ to R ₁₀₇ are the same or different and are selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl and substituted or unsubstituted C1-C30 alkoxy; or R ₁₀₄ to R ₁₀₇ may be linked to adjacent substituents to form a substituted or unsubstituted ring;

R ₂₀₁ to R ₂₁₁ each independently represents any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C30 alkoxy; or R201 to R211 may be linked to an adjacent substituent to form a substituted or unsubstituted ring;

The k is selected from 1,2 or 3.

Preferably, the doping material has the following structure:

The organic electroluminescent device according to the present invention may be provided with a plurality of light emitting layer stacks including at least one of the light emitting layers 3. The plurality of light emitting layers included in the light emitting layer stack may each emit light of different colors from each other or emit light of the same color. That is, the light emission color may be changed according to the substance constituting the light emitting layer. For example, the plurality of light-emitting layer stacks may contain substances that emit light of blue, green, red, yellow, white, or the like, and may be formed using phosphorescence or a fluorescent substance. At this time, the colors emitted from the respective light emitting layers may be in a complementary color relationship with each other. In addition, the colors may be selected in accordance with a combination of colors that can emit white light.

Electron transport region

In the organic electroluminescent device 100 according to the present invention, the electron transport region 5 functions to move electrons injected from the cathode 2 to the light emitting layer 3.

The electron transport region 5 includes a hole blocking layer 9, and at least one of an electron injection layer 11 and an electron transport layer 10.

The electron transport region 5 may have a structure of a hole blocking layer 9, an electron injection layer 11, an electron transport layer 10, a hole blocking layer 9 and an electron injection layer 11, an electron transport layer 10 and an electron injection layer 11, a hole blocking layer 9 and an electron transport layer 10, or a structure of a hole blocking layer 9, an electron transport layer 10 and an electron injection layer 11 with the light emitting layer 3 as a reference. Preferably, the electron transport region 5 includes a hole blocking layer 9, an electron transport layer 10, and an electron injection layer 11.

In the organic electroluminescent device 100 according to the present invention, the hole blocking layer 9 is preferably made of a material having good hole blocking properties, and specific examples of the material of the hole blocking layer 9 that can be used in the present invention may include imidazoles, triazoles, phenanthroline derivatives, quinolines, etc., such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] benzene (tmppb), 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- (naphthalen-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (HNBphen), 8-hydroxyquinoline (LiQ), etc., but are not limited thereto.

In the organic electroluminescent device 100 according to the present invention, the electron transport layer 10 is preferably made of a material having a high electron withdrawing ability and low HOMO and LUMO energy levels, and specific examples of the material of the electron transport layer 10 that can be used in the present invention may include imidazoles, triazoles, phenanthroline derivatives, quinolines, etc., 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 (TAZ), and the like, but is not limited thereto.

In the organic electroluminescent device 100 according to the present invention, the electron injection layer 11 is preferably formed of a material having a small potential barrier to an adjacent organic transport material and an effect of injecting electrons from a cathode, and specific examples of the material of the electron injection layer 11 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 (such as Al ₂O₃、MoO₃), but are not limited thereto.

Cathode electrode

In the organic electroluminescent device 100 according to the present invention, the cathode 2 preferably uses a low work function material capable of promoting electron injection into the organic layer, and specific examples of the cathode 2 material that can be used in the present invention may include metals such as aluminum, magnesium, silver, indium, tin, titanium, etc., and alloys thereof; the multilayered metal material is, for example, liF/Al, mg/Ag, li/Al, liO ₂/Al、BaF₂/Al, etc., but is not limited thereto.

The organic electroluminescent device 100 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 arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, and the like, but are not limited thereto.

The organic electroluminescent device 100 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 electrodes 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, etc., but are not limited thereto. The substrate may remain in a light emitting device or an electronic apparatus using the organic electroluminescent device of the present invention, or may serve as a support only in a manufacturing process of the organic electroluminescent device without remaining in a final product.

However, the structure of the organic electroluminescent device 100 according to the present invention is not limited thereto. The organic electroluminescent device 100 according to the present invention may be selected and combined according to device parameter requirements and material characteristics, or may add or omit part of organic layers, or may make organic layers having the same function into a laminated structure of two or more layers.

The light emitting type of the organic electroluminescent device 100 according to the present invention may be a top emitting device or a bottom emitting device, which are different in that the light emitting direction of the device is a direction of emitting light through the substrate or away from the substrate. For a bottom emission device, the light emitting direction of the device is through the substrate emission; for top-emitting devices, the light exiting direction of the device is the direction away from the substrate.

The structure of the organic electroluminescent device 100 of the present invention may be a positive structure or an inverted structure, which are different in the order of manufacturing the organic layers, specifically: the positive structure is that a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a luminescent layer, an electron blocking layer, a hole transport layer, a hole injection layer and an anode are sequentially formed on a substrate, and the negative structure is that an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode are sequentially formed on a substrate.

The organic electroluminescent device 100 according to 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 100 of the present invention can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps, etc.

The present invention is explained more fully by the following examples, but is not intended to be limited thereby. 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 burden.

The invention also provides a preparation method of the carbazole derivative represented by the formula 1 and the heterocyclic derivative represented by the formula 2, but the preparation method of the invention is not limited to the method. The core structure of the compounds of formula 1, formula 2 may be prepared by the reaction schemes shown below, substituents may be bonded by methods known in the art, and the kinds and positions of substituents or the number of substituents may be changed according to techniques known in the art.

Preparation of formula 1:

Preparation of formula 2:

description of the starting materials, reagents and characterization equipment:

the raw materials and reagent sources used in the following examples are not particularly limited, and may be commercially available products or prepared by methods well known to those skilled in the art. The raw materials and the reagents used in the invention are all reagent pure.

The mass spectrum uses a Wotes G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer in UK, chloroform as a solvent;

The elemental analysis uses a Vario EL cube type organic elemental analyzer of Elementar, germany, and the mass of the sample is 5-10 mg; synthesis of intermediates

Synthesis example 1 Synthesis of Compounds 1 to 5

Preparation of intermediate 1-5-A:

1-5-a (100.00 mmol,27.94 g), 1, 10-phenanthroline (20.00 mmol,3.60 g) and anhydrous K₃PO₄(200.00mmol,42.45g),1-5-b(100.00mmol,19.15g),DMSO(300.00ml),CuI(20.00mmol,3.81g), are added into a reaction flask under the protection of nitrogen, heated and stirred, and reflux reacted for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, quenched with water, extracted with chloroform, and an organic phase was added with a small amount of activated carbon, heated under reflux for 0.5 hour for decolorization, filtered, the solvent was removed under reduced pressure, and then column chromatography was performed with the mobile phase being methylene chloride: petroleum ether (1:5) to obtain 1-5-A (30.42 g, 78%), the purity of the solid detected by HPLC is more than or equal to 99.73%.

Preparation of intermediate 1-5-B:

1-5-A (70.00 mmol,27.30 g), 1-5-c (70.00 mmol,17.17 g), sodium t-butoxide (105.00 mmol,10.09 g), toluene (250.00 mL), palladium acetate (0.70 mmol,0.16 g), tri-t-butylphosphine (1.05 mmol,0.21 g) were added to the flask under nitrogen protection, and dissolved by stirring, followed by reflux reaction for 4.5 hours. After the reaction was completed, the reaction solution was cooled to room temperature, water was added, extraction was performed with methylene chloride, the organic phase was dried over anhydrous magnesium sulfate, filtration was performed, the solvent was removed under reduced pressure, and recrystallization was performed with toluene: methanol=8:1 to obtain 1-5-B (31.44 g, yield 75%), and the purity of the solid was not less than 99.83% by HPLC detection.

Preparation of Compounds 1-5:

1-5-B (35.00 mmol,20.96 g), 1-5-d (35.00 mmol,7.25 g), sodium t-butoxide (70.00 mmol,6.73 g), toluene (250.00 mL), dibenzylideneacetone dipalladium (0.35 mmol,0.32 g) and tri-t-butylphosphine (0.70 mmol,0.14 g) were added to the flask under nitrogen, dissolved with stirring, and reacted under reflux for 7.5 hours. After the completion of the reaction, 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, filtration was performed, the solvent was removed under reduced pressure, and recrystallization was performed with toluene to obtain Compound 1-5 (19.54 g, yield 77%), and the purity of the solid was not less than 99.96% as measured by HPLC. Mass spectrum m/z:724.3828 (theoretical value: 724.3817). Theoretical element content (%) C ₅₄H₄₈N₂: c,89.46; h,6.67; n,3.86. Measured element content (%): c,89.47; h,6.65; n,3.88.

Synthesis example 2 Synthesis of Compounds 1 to 25

Preparation of intermediate 1-25-d:

Under the protection of nitrogen, 1-25-e(70.00mmol,17.95g)、1-25-f(70.00mmol,14.49g)、Pd(PPh₃)₄(1.40mmol,1.62g)、K₂CO₃(140.00mmol,19.35g) mL of toluene, 100mL of ethanol and 100mL of water are added into a reaction bottle, the mixture is stirred, and the reactant system is heated and refluxed for 2.5 hours; after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=4: 1 recrystallisation to give 1-25-d (18.97 g, 80% yield); the purity of the solid detected by HPLC is not less than 99.21 percent. Mass spectrum m/z:338.0851 (theoretical value: 338.0862).

Preparation of Compounds 1-25:

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-25-a,1-5-b was replaced with equimolar 1-25-b,1-5-c was replaced with equimolar 1-25-c, and 1-5-d was replaced with equimolar 1-25-d, to give 1-25 (19.76 g, yield 74%), and the purity of the solid was not less than 99.97% as measured by HPLC. Mass spectrum m/z:762.3047 (theoretical value: 762.3035). Theoretical element content (%) C ₅₈H₃₈N₂: c,91.31; h,5.02; n,3.67. Measured element content (%): c,91.33; h,5.01; n,3.69.

Synthesis example 3 Synthesis of Compounds 1 to 69

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-25-b,1-5-c was replaced with equimolar 1-69-c, and 1-5-d was replaced with equimolar 1-69-d, to give 1-69 (17.89 g), and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:709.3485 (theoretical value: 709.3474). Theoretical element content (%) C ₅₃H₃₁D₇N₂: c,89.67; h,6.39; n,3.95. Measured element content (%): c,89.69; h,6.38; n,3.97.

Synthesis example 4 Synthesis of Compounds 1-131

According to the production method of Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-131-b,1-5-c was replaced with equimolar 1-131-c, and 1-5-d was replaced with equimolar 1-131-d, whereby 1-131 (18.29 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:696.3395 (theoretical value: 696.3381). Theoretical element content (%) C ₅₂H₂₈D₈N₂: c,89.62; h,6.36; n,4.02. Measured element content (%): c,89.63; h,6.33; n,4.05.

Synthesis example 5 Synthesis of Compounds 1-151

According to the production method of Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-25-c, and 1-5-d was replaced with equimolar 1-151-d, to give 1-151 (18.81 g), and the purity of the solid as measured by HPLC was not less than 99.98%. Mass spectrum m/z:688.2888 (theoretical value: 688.2878). Theoretical element content (%) C ₅₂H₃₆N₂: c,90.67; h,5.27; n,4.07. Measured element content (%): c,90.69; h,5.28; n,4.05.

Synthesis example 6 Synthesis of Compounds 1 to 153

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-153-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-25-c, and 1-5-d was replaced with equimolar 1-151-d, to give 1-153 (22.76 g), and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:928.3830 (theoretical value: 928.3817). Theoretical element content (%) C ₇₁H₄₈N₂: c,91.78; h,5.21; n,3.01. Measured element content (%): c,91.77; h,5.23; n,3.03.

Synthesis example 7 Synthesis of Compounds 1-155

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-155-c, and 1-5-d was replaced with equimolar 1-151-d, to give 1-155 (20.17 g), and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:778.2424 (theoretical value: 778.2407). Theoretical element content (%) C ₅₂H₃₁F₅N₂: c,80.19; h,4.01; n,3.60. Measured element content (%): c,80.18; h,4.03; n,3.63.

Synthesis example 8 Synthesis of Compounds 1-171

According to the production method of Synthesis example 1, 1-5-a was replaced with 1-171-a in equimolar amount, 1-5-b was replaced with 1-171-b in equimolar amount, 1-5-c was replaced with 1-171-c in equimolar amount, and 1-5-d was replaced with 1-171-d in equimolar amount, whereby 1-171 (20.20 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:812.2951 (theoretical value: 812.2940). Theoretical element content (%) C ₆₀H₃₆N₄: c,88.64; h,4.46; n,6.89. Measured element content (%): c,88.65; h,4.47; n,6.86.

Synthesis example 9 Synthesis of Compounds 1-203

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-203-c, and 1-5-d was replaced with equimolar 1-131-d, to give 1-203 (19.76 g), and the purity of the solid as measured by HPLC was not less than 99.98%. Mass spectrum m/z:742.3296 (theoretical value: 742.3286). Theoretical element content (%) C ₅₆H₃₄D₄N₂: c,90.53; h,5.70; n,3.77. Measured element content (%): c,90.51; h,5.72; n,3.78.

Synthesis example 10 Synthesis of Compounds 1 to 223

According to the production method of Synthesis example 1, 1-5-a was replaced with equimolar 1-153-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-223-c, and 1-5-d was replaced with equimolar 1-171-d, to give 1-223 (24.86 g), and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:1028.4119 (theoretical value: 1028.4130). Theoretical element content (%) C ₇₉H₅₂N₂: c,92.19; h,5.09; n,2.72. Measured element content (%): c,92.18; h,5.08; n,2.75.

Synthesis example 11 Synthesis of Compounds 1 to 271

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-271-b,1-5-c was replaced with equimolar 1-271-c, and 1-5-d was replaced with equimolar 1-271-d, to give 1-271 (19.90 g), and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:778.3333 (theoretical value: 778.3348). Theoretical element content (%) C ₅₉H₄₂N₂: c,90.97; h,5.43; n,3.60. Measured element content (%): c,90.95; h,5.47; n,3.63.

Synthesis example 12 Synthesis of Compounds 1 to 272

According to the production method of Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-272-b,1-5-c was replaced with equimolar 1-203-c, and 1-5-d was replaced with equimolar 1-151-d, to give 1-272 (20.92 g), and the purity of the solid as measured by HPLC was not less than 99.98%. Mass spectrum m/z:746.3550 (theoretical value: 746.3537). Theoretical element content (%) C ₅₆H₃₀D₈N₂: c,90.04; h,6.21; n,3.75. Measured element content (%): c,90.05; h,6.23; n,3.73.

Synthesis example 13 Synthesis of Compounds 1 to 288

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-153-a,1-5-b was replaced with equimolar 1-288-b,1-5-c was replaced with equimolar 1-288-c, and 1-5-d was replaced with equimolar 1-151-d, to give 1-288 (23.31 g), and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:924.3112 (theoretical value: 924.3128). Theoretical element content (%) C ₆₅H₄₀F₄N₂: c,84.40; h,4.36; n,3.03. Measured element content (%): c,84.38; h,4.38; n,3.02.

Synthesis example 14 Synthesis of Compounds 1 to 295

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-295-c, and 1-5-d was replaced with equimolar 1-295-d, to give 1-295 (22.76 g), and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:928.3830 (theoretical value: 928.3817). Theoretical element content (%) C ₇₁H₄₈N₂: c,91.78; h,5.21; n,3.01. Measured element content (%): c,91.77; h,5.20; n,3.08.

Synthesis example 15 Synthesis of Compounds 1-301

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-301-c, and 1-5-d was replaced with equimolar 1-151-d, to give 1-301 (24.95 g), and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:962.4614 (theoretical value: 962.4600). Theoretical element content (%) C ₇₃H₅₈N₂: c,91.02; h,6.07; n,2.91. Measured element content (%): c,91.03; h,6.08; n,2.85.

Synthesis example 16 Synthesis of Compounds 1 to 309

According to the production method of Synthesis example 1, 1-5-a was replaced with equimolar 1-309-a,1-5-b was replaced with equimolar 1-151-b,1-5-c was replaced with equimolar 1-309-c, and 1-5-d was replaced with equimolar 1-171-d, to give 1-309 (19.20 g), and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:721.3326 (theoretical value: 721.3333). Theoretical element content (%) C ₅₃H₂₇D₈N₃: c,88.18; h,6.00; n,5.82. Measured element content (%): c,88.16; h,6.03; n,5.85.

Synthesis example 17 Synthesis of Compounds 1 to 317

According to the production method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-317-b,1-5-c was replaced with equimolar 1-317-c, and 1-5-d was replaced with equimolar 1-151-d, to give 1-317 (19.53 g), and the purity of the solid as measured by HPLC was not less than 99.98%. Mass spectrum m/z:774.3982 (theoretical value: 774.3974). Theoretical element content (%) C ₅₈H₅₀N₂: c,89.88; h,6.50; n,3.61. Measured element content (%): c,89.87; h,6.51; n,3.63.

Synthesis example 18 Synthesis of Compounds 1 to 344

According to the production method in Synthesis example 1, 1-5-a was replaced with 1-69-a in equimolar amount, 1-5-b was replaced with 1-344-b in equimolar amount, and 1-5-c was replaced with 1-344-c in equimolar amount, whereby 1-344 (20.85 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:850.3330 (theoretical value: 850.3348). Theoretical element content (%) C ₆₅H₄₂N₂: c,91.73; h,4.97; n,3.29. Measured element content (%): c,91.74; h,4.95; n,3.28.

Synthesis example 19 Synthesis of Compounds 1 to 392

According to the production method in Synthesis example 2, 1-25-e was replaced with equimolar 1-392-e,1-25-f was replaced with equimolar 1-392-f,1-25-a was replaced with equimolar 1-69-a,1-25-b was replaced with equimolar 1-344-b,1-25-c was replaced with equimolar 1-392-c, and 1-25-d was replaced with equimolar 1-392-d, to give 1-392 (21.92 g), and the purity of the solid was 99.95% by HPLC detection. Mass spectrum m/z:920.4028 (theoretical value: 920.4038). Theoretical element content (%) C ₇₀H₄₀D₆N₂: c,91.27; h,5.69; n,3.04. Measured element content (%): c,91.28; h,5.68; n,3.08.

Synthesis example 20 Synthesis of Compounds 1-424

According to the production method of Synthesis example 1, 1-5-a was replaced with equimolar 1-424-a,1-5-b was replaced with equimolar 1-424-b,1-5-c was replaced with equimolar 1-424-c, and 1-5-d was replaced with equimolar 1-424-d, to give 1-424 (22.17 g), and the purity of the solid as measured by HPLC was not less than 99.98%. Mass spectrum m/z:855.3484 (theoretical value: 855.3473). Theoretical element content (%) C ₆₂H₃₅D₅F₂N₂: c,86.99; h,5.30; n,3.27. Measured element content (%): c,86.97; h,5.28; n,3.28.

Preparation of intermediate 2-1-B

Synthetic intermediate 2-1-A

2-1-A (24.66 g,120.00 mmol) is added into a reaction bottle under the protection of nitrogen, the bisboronic acid pinacol ester (30.47g,120.00mmol),Pd(PPh₃)₄(2.31g,2.00mmol)、K₂CO₃(24.88g,180.00mmol),DMF(500.00mL), is heated for 2.5 hours, distilled water is added after the reaction is finished, dichloromethane is used for extraction, liquid separation is carried out, an organic phase is washed three times by distilled water, anhydrous magnesium sulfate is dried, a solvent is concentrated by rotary evaporation, cooling crystallization and suction filtration are carried out, and the obtained solid is treated by toluene: ethanol=4: 1 to give intermediate 2-1-A (23.94 g, yield 79%); HPLC purity is not less than 98.81%. Mass spectrum m/z:252.1072 (theoretical value: 252.1088).

Synthetic intermediate 2-1-B

Intermediate 2-1-A (22.73 g,90.00 mmol) and raw material 2-1-b(25.46g,90.00mmol)、K₂CO₃(19.35g,140.00mmol)、Pd(PPh₃)₄(1.16g,1.00mmol), were added sequentially to a reaction flask under nitrogen protection, 400mL of toluene/ethanol/water (2:1:1) mixed solvent was added, the mixture was stirred, and the above reactant system was heated under reflux for 2 hours. After the reaction was completed, cooling to room temperature, adding toluene and separating the phases, washing the toluene phase three times with distilled water, drying over anhydrous magnesium sulfate, rotary evaporating the concentrated solvent, cooling to crystallize, suction filtering, and subjecting the obtained solid to toluene: ethanol=20: 3 to give intermediate 2-1-B (20.27 g, yield 80%). HPLC purity is more than or equal to 99.83%. Mass spectrum m/z:279.9667 (theoretical value: 279.9654).

According to the above procedure, equimolar substitution of starting materials 2-1-a and 2-1-b was performed, the following intermediates were synthesized:

synthesis example 21 Synthesis of Compound 2-1

Preparation of intermediate 2-1-C:

Raw materials 2-1-c (39.73 g,100.00 mmol) were sequentially added to a reaction flask under nitrogen protection, the bisboronic acid pinacol ester (25.39g,100.00mmol),Pd(PPh₃)₄(1.73g,1.50mmol)、K₂CO₃(30.41g,220.00mmol),DMF(400.00mL), was then heated to react for 4 hours, after the reaction was completed, cooled to room temperature, 500.00mL of water was added thereto, followed by extraction with ethyl acetate (500.00 ml×3), the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed by rotary evaporation, and toluene was used: ethanol=20: 1 recrystallisation and drying to give intermediate 2-1-C (37.77 g, 85% yield); HPLC purity is not less than 98.70%. Mass spectrum m/z:444.2275 (theoretical value: 444.2261).

Preparation of intermediate 2-1-D:

Under the protection of nitrogen, sequentially adding an intermediate 2-1-C (31.11 g,70.00 mmol), raw materials 2-1-B(19.71g,70.00mmol)、Pd(PPh₃)₄(1.39g,1.20mmol)、K₂CO₃(13.82g,100.00mmol), 300.00mL of toluene, 100mL of ethanol and 100mL of water into a reaction bottle, stirring the mixture, and heating and refluxing the system for reaction for 3.5 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate 2-1-D (27.98 g, yield 77%); HPLC purity is more than or equal to 99.45%. Mass spectrum m/z:518.1818 (theoretical value: 518.1801).

Preparation of intermediate 2-1-E:

To a reaction flask, under nitrogen protection, intermediate 21-D (25.95 g,50.00 mmol), pinacol ester of biboronate (12.70 g,50.00 mmol), KOAc (10.80 g,110.00 mmol), pd (dppf) Cl ₂ (0.73 g,1.00 mmol), 1, 4-dioxane (350.00 mL) were added sequentially, then heated to reflux temperature for 4.5 hours, after completion of the reaction, cooled to room temperature, 350.00mL of water was added thereto, then extracted with ethyl acetate (500.00 mL. Times.3), the organic layer was dried over anhydrous MgSO ₄, ethyl acetate was distilled off by spin-evaporation, then recrystallized using toluene, and dried to give intermediate 2-1-E (24.12 g, yield 79%); HPLC purity is more than or equal to 99.83%. Mass spectrum m/z:610.3033 (theoretical value: 610.3043).

Preparation of Compound 2-1:

Under the protection of nitrogen, sequentially adding an intermediate 2-1-E (18.32 g,30.00 mmol), a raw material 2-1-d(5.94g,30.00mmol)、Pd₂(dba)₃(0.46g,0.50mmol)、P(t-Bu)₃(0.30g,1.50mmol),K₂CO₃(6.91g,50.00mmol) and 150.00mL of tetrahydrofuran into a reaction bottle, stirring the mixture, and heating and refluxing the reactant system for 5 hours; after the completion of the reaction, cooled to room temperature, water was added, extracted with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and recrystallized from toluene to give compound 2-1 (13.90 g, yield 77%); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:601.2418 (theoretical value: 601.2406). Theoretical element content (%) C ₄₅H₃₁ NO: c,89.82; h,5.19; n,2.33. Measured element content (%): c,89.85; h,5.15; n,2.36.

Synthesis example 22 Synthesis of Compounds 2-35

Using the same method as in example 21, 2-35 (11.42 g) was synthesized by substituting 2-1-c with equimolar 2-35-c and 2-1-B with equimolar 2-35-B, and the solid purity was ≡ 99.96% by HPLC. Mass spectrum m/z:507.2370 (theoretical value: 507.2359). Theoretical element content (%) C ₃₆H₂₁D₅N₂ O: c,85.18; h,6.15; n,5.52. Measured element content (%): c,85.16; h,6.18; n,5.53.

Synthesis example 23 Synthesis of Compounds 2 to 106

Using the same method as in example 21, 2-106 (14.22 g) was synthesized by substituting 2-1-B with equimolar 2-106-B and 2-1-d with equimolar 2-106-d, and the purity of the solid was ≡ 99.97% by HPLC. Mass spectrum m/z:615.2573 (theoretical value: 615.2562). Theoretical element content (%) C ₄₆H₃₃ NO: c,89.73; h,5.40; n,2.27. Measured element content (%): c,89.75; h,5.43; n,2.23.

Synthesis example 24 Synthesis of Compounds 2-123

Using the same method as in example 21, 2-123 (16.74 g) was synthesized by substituting equimolar 2-123-c for 2-1-c and equimolar 2-123-B for 2-1-B, and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:743.2823 (theoretical value: 743.2811). Theoretical element content (%) C ₅₀H₃₇F₄ NO: c,80.74; h,5.01; n,1.88. Measured element content (%): c,80.75; h,5.02; n,1.85.

Synthesis example 25 Synthesis of Compounds 2-162

Using the same method as in example 21, 2-162-B was replaced with equimolar 2-162-B, and compound 2-162 (14.77 g) was synthesized, and the purity of the solid was ≡ 99.97% by HPLC. Mass spectrum m/z:647.3138 (theoretical value: 647.3126). Theoretical element content (%) C ₄₈H₃₃D₄ NO: c,88.99; h,6.38; n,2.16. Measured element content (%): c,88.95; h,6.41; n,2.18.

Synthesis example 26 Synthesis of Compounds 2-287

Using the same method as in example 21, 2-1-B was replaced with equimolar 2-287-B and 2-1-d was replaced with equimolar 2-287-d. Compound 2-287 (16.16 g) was synthesized with a purity of > 99.96% as measured by HPLC. Mass spectrum m/z:727.2883 (theoretical value: 727.2875). Theoretical element content (%) C ₅₅H₃₇ NO: c,90.75; h,5.12; n,1.92. Measured element content (%): c,90.72; h,5.16; n,1.95.

Synthesis example 27 Synthesis of Compounds 2-326

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-326-c, and 2-1-B was replaced with equimolar 2-326-B. Compound 2-326 (11.60 g) was synthesized and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:495.2518 (theoretical value: 495.2500). Theoretical element content (%) C ₃₆H₂₅D₄ NO: c,87.24; h,6.71; n,2.83. Measured element content (%): c,87.23; h,6.73; n,2.85.

Synthesis example 28 Synthesis of Compounds 2-341

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-341-c, 2-1-B was replaced with equimolar 2-341-B, and 2-1-d was replaced with equimolar 2-341-d. Compound 2-341 (16.37 g) was synthesized and the purity of the solid was ≡ 99.94% by HPLC. Mass spectrum m/z:757.4233 (theoretical value: 757.4222). Theoretical element content (%) C ₅₆H₄₇D₄ NO: c,88.73; h,7.31; n,1.85. Measured element content (%): c,88.75; h,7.33; n,1.83.

Synthesis example 29 Synthesis of Compounds 2-377

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-377-c, 2-1-B was replaced with equimolar 2-377-B, and 2-1-d was replaced with equimolar 2-377-d. Compound 2-377 (13.67 g) was synthesized with a purity of 99.97% as determined by HPLC. Mass spectrum m/z:641.2118 (theoretical value: 641.2103). Theoretical element content (%) C ₄₅H₂₇N₃O₂: c,84.22; h,4.24; n,6.55. Measured element content (%): c,84.23; h,4.23; n,6.51.

Synthesis example 30 Synthesis of Compounds 2-394

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-394-c, 2-1-B was replaced with equimolar 2-394-B, and 2-1-d was replaced with equimolar 2-394-d. Compound 2-394 (13.14 g) was synthesized with a purity of > 99.96% as measured by HPLC. Mass spectrum m/z:591.2551 (theoretical value: 591.2562). Theoretical element content (%) C ₄₄H₃₃ NO: c,89.31; h,5.62; n,2.37. Measured element content (%): c,89.28; h,5.63; n,2.38.

Synthesis example 31 Synthesis of Compounds 2 to 415

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-415-c, 2-1-B was replaced with equimolar 2-415-B, and 2-1-d was replaced with equimolar 2-415-d. Compound 2-415 (16.37 g) was synthesized and the purity of the solid was ≡ 99.98% by HPLC. Mass spectrum m/z:717.3985 (theoretical value: 717.3971). Theoretical element content (%) C ₅₃H₅₁ NO: c,88.66; h,7.16; n,1.95. Measured element content (%): c,88.65; h,7.18; n,1.91.

Synthesis example 32 Synthesis of Compounds 2-474

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-474-c, 2-1-B was replaced with equimolar 2-474-B, and 2-1-d was replaced with equimolar 2-474-d. Compound 2-474 (14.59 g) was synthesized and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:694.2451 (theoretical value: 694.2443). Theoretical element content (%) C ₅₀H₃₄N₂ S: c,86.42; h,4.93; n,4.03. Measured element content (%): c,86.43; h,4.95; n,4.02.

Synthesis example 33 Synthesis of Compounds 2-505

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-505-c, 2-1-B was replaced with equimolar 2-505-B, and 2-1-d was replaced with equimolar 2-287-d. Compound 2-505 (15.33 g) was synthesized and the purity of the solid was ≡ 99.96% by HPLC. Mass spectrum m/z:699.2572 (theoretical value: 699.2562). Theoretical element content (%) C ₅₃H₃₃ NO: c,90.96; h,4.75; n,2.00. Measured element content (%): c,90.95; h,4.72; n,2.03.

Synthesis example 34 Synthesis of Compounds 2-518

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-518-c, 2-1-B was replaced with equimolar 2-518-B, and 2-1-d was replaced with equimolar 2-518-d. Compound 2-518 (14.88 g) was synthesized and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:688.2923 (theoretical value: 688.2912). Theoretical element content (%) C ₄₉H₄₀N₂ S: c,85.43; h,5.85; n,4.07. Measured element content (%): c,85.42; h,5.88; n,4.08.

Synthesis example 35 Synthesis of Compounds 2-526

Using the same method as in example 21, 2-1-B was replaced with equimolar 2-526-B, and 2-1-d was replaced with equimolar 2-106-d. Compound 2-526 (16.63 g) was synthesized with a purity of > 99.97% as measured by HPLC. Mass spectrum m/z:719.3195 (theoretical value: 719.3188). Theoretical element content (%) C ₅₄H₄₁ NO: c,90.09; h,5.74; n,1.95. Measured element content (%): c,90.08; h,5.72; n,1.96.

Synthesis example 36 Synthesis of Compounds 2-550

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-550-c, 2-1-B was replaced with equimolar 2-550-B, and 2-1-d was replaced with equimolar 2-550-d. Compound 2-550 (13.56 g) was synthesized and the purity of the solid was ≡ 99.96% by HPLC. Mass spectrum m/z:664.2891 (theoretical value: 664.2878). Theoretical element content (%) C ₅₀H₃₆N₂: c,90.33; h,5.46; n,4.21. Measured element content (%): c,90.28; h,5.47; n,4.23.

Synthesis example 37 Synthesis of Compounds 2-586

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-586-c, 2-1-B was replaced with equimolar 2-586-B, and 2-1-d was replaced with equimolar 2-586-d. Compound 2-586 (14.40 g) was synthesized and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:695.3138 (theoretical value: 695.3128). Theoretical element content (%) C ₅₀H₃₃D₃N₄: c,86.30; h,5.65; n,8.05. Measured element content (%): c,86.28; h,5.66; n,8.07.

Synthesis example 38 Synthesis of Compounds 2-604

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-604-c, 2-1-B was replaced with equimolar 2-604-B, and 2-1-d was replaced with equimolar 2-604-d. Compound 2-604 (12.26 g) was synthesized with a purity of > 99.97% as measured by HPLC. Mass spectrum m/z:575.2569 (theoretical value: 575.2554). Theoretical element content (%) C ₄₁H₂₅D₆ NS: c,85.52; h,6.48; n,2.43. Measured element content (%): c,85.51; h,6.47; n,2.47.

Synthesis example 39 Synthesis of Compound 2-629

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-629-c, 2-1-B was replaced with equimolar 2-629-B, and 2-1-d was replaced with equimolar 2-629-d. Compound 2-629 (12.49 g) was synthesized and the purity of the solid was not less than 99.98% by HPLC. Mass spectrum m/z:594.1885 (theoretical value: 594.1878). Theoretical element content (%) C ₄₀H₂₆N₄ S: c,80.78; h,4.41; n,9.42. Measured element content (%): c,80.77; h,4.43; n,9.45.

Synthesis example 40 Synthesis of Compounds 2-661

Using the same method as in example 21, 2-1-c was replaced with equimolar 2-505-c, 2-1-B was replaced with equimolar 2-661-B, and 2-1-d was replaced with equimolar 2-106-d. Compound 2-661 (15.49 g) was synthesized with a purity of > 99.97% as determined by HPLC. Mass spectrum m/z:7.3358 (theoretical value: 697.3345). Theoretical element content (%) C ₅₂H₄₃ NO: c,89.49; h,6.21; n,2.01. Measured element content (%): c,89.47; h,6.23; n,2.03.

Device examples 1 to 20

The ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporation HI is carried out on the ITO substrate as a hole injection layer, and the evaporation thickness is 15nm; vacuum evaporation HT is carried out on the hole injection layer to serve as a hole transport layer, and the evaporation thickness is 80nm; a mixture of the inventive compounds 1 to 5 (first host) and the inventive compounds 2 to 586 (second host) in a weight ratio of 5:5 was used as host, and a host material was vacuum-evaporated on the hole transport layer: dopant D-18=92:8 (mass ratio) as light-emitting layer, evaporation thickness 20nm; vacuum evaporating ET on the luminous layer as an electron transport layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.

Device examples 2 to 20: an organic electroluminescent device was produced by the same procedure as in device example 1, except that inventive compounds 1-25、1-69、1-131、1-151、1-153、1-155、1-171、1-203、1-223、1-271、1-272、1-288、1-295、1-301、1-309、1-317、1-344、1-392、1-424 were used as the first host material in place of inventive compounds 1-5 in device example 1, respectively, and inventive compounds 2-394、2-518、2-326、2-106、20162、2-341、2-629、2-1、2-415、2-377、2-526、2-123、2-35、2-661、2-505、2-474、2-287、2-604、2-550 were used as the second host material in place of inventive compounds 2-586 in device example 1, respectively.

Comparative example 1: the ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporation HI is carried out on the ITO substrate as a hole injection layer, and the evaporation thickness is 15nm; vacuum evaporation HT is carried out on the hole injection layer to serve as a hole transport layer, and the evaporation thickness is 80nm; vacuum evaporation of inventive compounds 1-69 on hole transport layer: dopant D-18=92:8 (mass ratio) as light-emitting layer, evaporation thickness 20nm; vacuum evaporating ET on the luminous layer as an electron transport layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.

Comparative examples 2 to 26: an organic electroluminescent device was produced by the same procedure as in comparative example 1, except that the compound 1-69, compound 1-151, compound 1-153, compound 1-155, compound 1-171, compound 1-203, compound 1-223, compound 1-271, compound 1-295, compound 1-301, compound 1-317, compound 1-344, compound 1-424, compound 2-1, compound 2-35, compound 2-106, compound 2-162, compound 2-287, compound 2-341, compound 2-377, compound 2-415, compound 2-474, compound 2-518, compound 2-550, compound 2-629 and compound 2-661 of the present invention in comparative example 1 were used as the host materials of the luminescent layer, respectively.

Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from MCSCIENCE was used. The environment tested was atmospheric and the temperature was room temperature.

The results of the luminescence characteristic test of the obtained organic electroluminescent device are shown in table 1. Table 1 shows the results of the luminescence characteristics test of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative substances.

Table 1 test of light emitting characteristics of organic electroluminescent device

As can be seen from the results in table 1, the organic electroluminescent device has higher luminous efficiency and longer device lifetime when the carbazole-based derivative represented by formula 1 and the heterocyclic-based derivative represented by formula 2 are used together as the host material of the light-emitting layer, as compared with comparative examples 1 to 26.

Device examples 21 to 40

The ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporation HI is carried out on the ITO substrate as a hole injection layer, and the evaporation thickness is 15nm; vacuum evaporation HT is carried out on the hole injection layer to serve as a hole transport layer, and the evaporation thickness is 80nm; a mixture of the inventive compounds 1 to 5 (first host) and the inventive compounds 2 to 586 (second host) in a weight ratio of 3:7 was used as host, and a host material was vacuum-evaporated on the hole transport layer: dopant D-36=95:5 (mass ratio) as light emitting layer, evaporation thickness 20nm; vacuum evaporating ET on the luminous layer as an electron transport layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.

Device examples 22 to 40: an organic electroluminescent device was produced by the same procedure as in device example 21, except that inventive compounds 1-25、1-69、1-131、1-151、1-153、1-155、1-171、1-203、1-223、1-271、1-272、1-288、1-295、1-301、1-309、1-317、1-344、1-392、1-424 were used as the first host material in place of inventive compounds 1-5 in device example 21, respectively, and inventive compounds 2-394、2-518、2-326、2-106、20162、2-341、2-629、2-1、2-415、2-377、2-526、2-123、2-35、2-661、2-505、2-474、2-287、2-604、2-550 were used as the second host material in place of inventive compounds 2-586 in device example 21, respectively.

Comparative example 27: the ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporation HI is carried out on the ITO substrate as a hole injection layer, and the evaporation thickness is 15nm; vacuum evaporation HT is carried out on the hole injection layer to serve as a hole transport layer, and the evaporation thickness is 80nm; vacuum evaporation of inventive compounds 1-5 on hole transport layer: dopant D-18=95:5 (mass ratio) as light-emitting layer, evaporation thickness 20nm; vacuum evaporating ET on the luminous layer as an electron transport layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.

Comparative examples 28 to 48: the same procedure as in comparative example 27 was used to prepare an organic electroluminescent device, except that the compound 1-5 of the present invention in comparative example 27 was replaced with the compound 1-25, compound 1-131, compound 1-151, compound 1-153, compound 1-155, compound 1-272, compound 1-288, compound 1-301, compound 1-309, compound 1-392, compound 2-106, compound 2-123, compound 2-162, compound 2-326, compound 2-341, compound 2-394, compound 2-505, compound 2-526, compound 2-586, compound 2-604 and compound 2-661, respectively, as a host material for the light-emitting layer.

The results of the luminescence characteristic test of the obtained organic electroluminescent device are shown in table 2. Table 2 shows the results of the test of the luminescence characteristics of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative substances.

Table 2 test of light emission characteristics of organic electroluminescent devices

As can be seen from the results in table 2, the devices of examples 21 to 40 exhibited higher luminous efficiency and longer device lifetime than those of comparative examples 27 to 48. The light-emitting layer is formed by combining the two materials, so that the carrier transmission in the light-emitting layer is balanced, the recombination probability of excitons in the light-emitting layer is greatly improved, and the light-emitting layer is used as a main material of the light-emitting layer in the organic electroluminescent device, so that the light-emitting efficiency of the device is improved, and the service life of the device is prolonged effectively.

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

Claims

1. An organic electroluminescent device comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a luminescent layer, the luminescent layer comprises a main body material and a doping material, and is characterized in that the main body material comprises carbazole derivatives shown in a formula 1 and heterocyclic derivatives shown in a formula 2,

in the formula 2, A is selected from any one of the structures shown below,

The z is the same or different and is selected from CRa or N;

The R ₆、R₇、R₈ is the same or different and is selected from any one of hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl and substituted or unsubstituted quinoxalinyl; the R ₆、R₇ groups may be linked to form a substituted or unsubstituted ring;

The L ₄ is selected from any one of the structures shown below,

the X ₁ is any one selected from O, S, NRb;

the x is the same or different and is selected from CRc or N;

2. An organic electroluminescent device as claimed in claim 1, wherein Ar ₁ is selected from any one of the structures shown below,

3. An organic electroluminescent device as claimed in claim 1, wherein L ₂、L₃ is the same or different and is selected from a single bond or any one of the structures shown below,

4. An organic electroluminescent device as claimed in claim 1, wherein theSelected from any one of the structures shown below,

5. The organic electroluminescent device as claimed in claim 1, wherein the carbazole derivative represented by formula 1 is selected from any one of structures shown below,

6. The organic electroluminescent device according to claim 1, wherein the heterocyclic derivative represented by formula 2 is selected from any one of the structures shown below,

7. An organic electroluminescent device as claimed in claim 1, wherein a is selected from any one of the structures shown below,

8. The organic electroluminescent device as claimed in claim 1, wherein L ₄ is the same or different and is selected from any one of the structures shown below,

The e ₁ are the same or different and are selected from 0, 1, 2, 3 or 4; the e ₂ are the same or different and are selected from 0, 1, 2, 3, 4, 5 or 6; the e ₃ are the same or different and are selected from 0, 1 or 2; the e ₄ are the same or different and are selected from 0, 1, 2 or 3; when two or more R9 s are present, the two or more R ₉ s are the same or different from each other; when two or more R ₉ 'are present, the two or more R ₉' are the same or different from each other;

9. An organic electroluminescent device as claimed in claim 1, wherein theSelected from any one of the structures shown below,

10. The organic electroluminescent device according to claim 1, wherein the heterocyclic derivative represented by formula 2 is selected from any one of the structures shown below,