CN115802781A

CN115802781A - Organic electroluminescent device

Info

Publication number: CN115802781A
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: 2023-03-14

Abstract

The invention provides an organic electroluminescent device, belonging 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 main material of the light-emitting layer, and the carbazole derivative and the heterocyclic derivative have similar physical properties and good carrier transport characteristics, so that when the carbazole derivative and the heterocyclic derivative are used as the main material of the light-emitting layer, the light-emitting 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, organic light-emitting diodes (OLEDs) have 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, etc., and as the OLED technology is increasingly improved and the cost is gradually reduced, the market demand of the OLEDs is increasing at an accelerated pace, and the OLEDs are widely applied to numerous fields such as display and lighting, and are one of novel display technologies with a development prospect and one of competitive hot spots in the international high and new technical fields.

The OLED includes an anode, a cathode, and organic layers 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 double-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 drive of an external voltage, and the excitons are radiated and excited to emit photons, so that a light-emitting phenomenon is generated.

The light-emitting layer is a key for improving the performance of the OLED, the light-emitting layer usually comprises a host material and a doping material, 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, the carrier transmission is balanced, exciton quenching is reduced, the light-emitting efficiency of the device is improved, and the service life of the device is prolonged.

Therefore, in the selection of the dual host materials, there are many factors that need to be paid attention to, rather than simply mixing the two materials with each other, not only the problem of energy level matching between the host materials of the materials needs to be considered, but also the balance between the hole transport and the electron transport needs to be considered, and only if the electron transport and the hole transport in the light emitting layer need to reach a proper balance, the maximum recombination of excitons in the light emitting layer can be achieved, so only by matching the proper materials, the light emitting efficiency and the service life of the device can be effectively improved.

Disclosure of Invention

The invention provides an organic light-emitting device, which aims to solve the problem that in the prior art, the hole and the electron of the organic light-emitting device are difficult to balance, so that the device performance is poor.

The invention provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a light-emitting layer, the light-emitting layer comprises a main material and a doping material, the main material comprises a carbazole derivative shown in a formula 1 and a heterocyclic derivative shown in a formula 2,

in the formula 1, L ₁ Any one selected from the structures shown below,

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

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

ar is ₁ Any one selected from substituted or unsubstituted C3-C12 alicyclic group and substituted or unsubstituted C6-C30 aryl group;

said L ₂ 、L ₃ The same or different 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 is ₁ The same or different is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, and substituted or unsubstituted C6-C30 aromatic groupAny one of the above groups;

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

the R is ₂ 、R ₃ Any one of the same or different hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, and substituted or unsubstituted C6-C18 aryl;

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

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

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

said Y is ₁ 、Y ₂ The same or different ones are selected from any one of CRzRy, NRx, O and S;

the Rz, the Ry and the 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 group 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 group and substituted or unsubstituted C6-C18 aryl; when two or more Ra are present, the 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;

said R is ₆ 、R ₇ 、R ₈ Any one of the same or different 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 is ₆ 、R ₇ May be linked to form a substituted or unsubstituted ring;

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

said L is ₄ Selected from any one of the structures shown below,

wherein at least one R ₉ Any one selected from 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 of R ₉ The same or different is selected from any one of hydrogen, deuterium, halogen and cyano;

said e ₁ Identical or different from 0,1, 2,3 or 4; said e ₂ Identical or different from 0,1, 2,3, 4,5 or 6; when two or more R's are present ₉ When two or more R are present ₉ Are the same or different from each other;

said X is ₁ Any one selected from O, S and NRb;

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

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

the Rc and R ₄ The same or different ones are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, 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 light-emitting 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 carbazole derivative and the heterocyclic derivative act together to ensure that hole transmission and electron transmission in the light-emitting layer reach proper balance, so that the recombination probability of excitons in the light-emitting layer is maximized, and meanwhile, 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 are jointly used as the main material of the light-emitting layer in the organic electroluminescent device, so that the light-emitting efficiency of the device can be improved, and the service life of the device can be effectively prolonged.

Drawings

Fig. 1 is a sectional view of the 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 clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. And the embodiments and features of the embodiments may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without inventive step, are within the scope of protection of the invention.

Unless defined otherwise, technical or scientific terms used herein have the same meaning as commonly 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 their natural isotopic abundance and unnatural abundance.

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

In the present 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 respective optional positions of the aromatic ring. For example, in the case of a liquid,

can represent

And so on.

In the present specification, when a bond at a substituent or attachment site extends through two or more rings, it indicates that it may be attached to either of the two or two rings, in particular to either of the respective optional sites of the rings. For example, in the case of a liquid,

can represent

Or

Can represent

Can represent

Or

Can represent

And so on.

The halogen in the invention refers to fluorine, chlorine, bromine and iodine;

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

The alicyclic ring in the present invention means a cyclic hydrocarbon having aliphatic properties, which contains a closed carbocyclic ring in its molecule, and may be a cycloalkane, cycloalkene, 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 cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, cyclopropane, cyclobuten, cyclopentene, cyclohexene, cycloheptene, etc., but are not limited thereto.

The alicyclic group in the present invention means a monovalent group obtained by removing 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, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc.

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

The arylene group is a divalent group formed by removing two hydrogen atoms from aromatic nucleus carbon of aromatic hydrocarbon molecules. The above description of the aryl group can be applied to them except that they are each a divalent group.

The alicyclic group in the present invention means a divalent group obtained by removing two hydrogen atoms from an alicyclic hydrocarbon molecule. In addition to being each a divalent group, the above description of the alicyclic group can be applied.

The heteroaryl group in the present invention is a general term for a monovalent group obtained by removing one hydrogen atom from a core atom of an aromatic heterocycle composed of carbon and a hetero atom. The hetero atom may be one or more of N, O, S, si, P, may be a monocyclic heteroaryl group or a fused 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, quinolyl, isoquinolyl, oxazolyl, thiazolyl, imidazolyl, benzothienyl, benzofuryl, benzoxazolyl, benzothiazolyl, benzimidazolyl, pyridooxazolyl, pyridoimidazolyl, pyrimidooxazolyl, pyrimidozolyl, pyrimidoimidazolyl, dibenzofuryl, dibenzothienyl, carbazolyl, phenazinyl, quinoxalyl, quinazolinyl, quinoxazolyl, quinolinozolyl, quinolinoimidazolyl, quinolinoiyl, purinyl, 2-purinyl, N-imidazolyl, and the like, but not limited thereto.

The heteroarylene group in the present invention is a divalent group obtained by removing two hydrogen atoms from a core atom of an aromatic heterocycle consisting of carbon and a hetero atom. The above description of heteroaryl groups applies in addition to divalent groups.

The "alkoxy group" in the present invention 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.

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

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

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

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

The connection to form a substituted or unsubstituted alicyclic ring according to the present invention means that two groups are connected 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 linkage may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, cycloheptene, but are not limited thereto.

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

In describing the structural elements of the present invention, the use of the terms "comprising" or "including" and the like in the present invention is intended to mean that the element or item preceding the term "comprises" or "comprising" and its equivalents, but not exclude the presence of other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "inner", "outer", "upper", "lower", and the like are used merely to indicate relative positional relationships, and when the absolute position of a described structural element is changed, the relative positional relationship may also be changed accordingly. When a component such as a layer, a film, a region, or a plate is located "on" another component, it is understood that the component is located not only "directly above" the other component but also in the middle. On the contrary, when one component is positioned "directly above" the other component, it is to be understood that no other component is present therebetween.

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 dopant material, and the host material includes a carbazole derivative shown in formula 1 and a heterocyclic derivative shown in formula 2.

In the organic electroluminescent device 100, the host material in the light-emitting layer 3 includes the carbazole derivative shown in formula 1 and the heterocyclic derivative shown in formula 2, and the carbazole derivative shown in formula 1 and the heterocyclic derivative have similar physical properties, and meanwhile, the carbazole derivative shown in formula 1 has a relatively wide energy gap and has good hole transport characteristics, and the heterocyclic derivative shown in formula 2 has a relatively narrow energy gap and has good electron transport characteristics, and the good carrier transport characteristics of the carbazole derivative and the heterocyclic derivative can enable carrier transport inside the light-emitting layer 3 to achieve proper balance, so that the recombination probability of excitons inside the light-emitting layer 3 is effectively improved, and further, the light-emitting efficiency and the service life of the organic electroluminescent device 100 are improved.

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

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); and conductive polymers such as poly (3-methylthiophene), polypyrrole, polyaniline, poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDT), and the like, but not limited thereto.

Organic material layer

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

Hole transport region

In the organic electroluminescent element 100 according to the present invention, the hole transport region 4 included therein functions 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 a structure including 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 an electron blocking layer 6, a hole transport layer 7 and a hole injection layer 8, with respect to the light-emitting layer 3. Preferably, the hole transport region 4 comprises an electron blocking layer 6, a hole transport layer 7 and a hole injection layer 8.

The hole injection layer 8 of the present invention is preferably formed using 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 metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, phthalocyanine compounds, benzidine compounds, phenazine compounds, and the like, such as copper phthalocyanine (CuPc), titanyl phthalocyanine, N '-diphenyl-N, N' -bis- [4- (N, N-diphenylamine) phenyl ] benzidine (npnpnpb), N '-tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), biquinoxalino [2,3-a:2',3'-c ] phenazine (HATNA), 4' -tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN), 4', 4' -tris (N, N-diphenylamino) triphenylamine (TDATA), etc., but is not limited thereto.

The hole transport layer 7 of 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, but are not limited to, diphenylamines, triphenylamines, fluorenes, carbazoles, and the like, such as N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-bis (naphthalene-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), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like.

The electron blocking layer 6 according to the present invention preferably uses a material having good electron blocking properties. Specific examples of the material of the electron blocking layer 6 that can be used in the present invention may include, but are not limited to, diphenylamine-based compounds, triphenylamine-based compounds, fluorene-based compounds, triarylamine-based compounds, and carbazole-based compounds, 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- [ di (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), and the like.

Luminescent 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 includes a host material and a dopant material, the mixing ratio of which can be adjusted within the range known in the art, the host material includes a carbazole-based derivative represented by formula 1 and a heterocyclic-based derivative represented by formula 2,

in the formula 1, L ₁ Any one selected from the structures shown below,

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

ar is ₁ Selected from substituted or unsubstituted C3-C12 alicyclic group, substituted or unsubstituted C6-C30 aromatic groupAny one of the above groups;

said L ₂ 、L ₃ The same or different one selected from single bond, substituted or unsubstituted C3-C12 alicyclic group, substituted or unsubstituted C6-C30 arylene group;

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

said R is ₂ 、R ₃ Any one of the same or different hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 alicyclic group, and substituted or unsubstituted C6-C18 aryl;

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

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

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

said R is ₆ 、R ₇ 、R ₈ Any one of the same or different 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; said R is ₆ 、R ₇ May be linked to form a substituted or unsubstituted ring;

said L is ₄ Selected from any one of the structures shown below,

wherein at least one R ₉ 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 of R ₉ The same or different is selected from any one of hydrogen, deuterium, halogen and cyano;

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

said X is ₁ Any one selected from O, S and NRb;

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

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

the Rc, the Rd and the 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 group and substituted or unsubstituted C6-C18 aryl; said Rc, rd may be joined to form a substituted or unsubstituted ring;

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

said g is ₁ The same or different is selected from 0,1, 2,3, 4 or 5; said g is ₂ Identical or different from 0,1, 2,3 or 4; g is described ₃ The same or different is selected from 0,1, 2,3, 4,5, 6 or 7; said g is ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7, 8 or 9; g is described ₅ Identical or different from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11; said g is ₆ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; when two or more are presentR is ₁₀ When two or more R are present 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, said R is ₁₀ Any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, and triphenylene, which may be the same or different; the R is ₁₀ May be substituted with one or more substituents which may be the same or different, selected from any one of deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, triphenylenyl; when two or more substituents are present, the two or more substituents may be the same as or different from each other, or adjacent R ₁₀ Are linked to each other to form a substituted or unsubstituted ring.

Preferably, said L ₂ 、L ₃ The same or different is selected from a single bond or any one of the structures shown below,

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

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

j is said ₁ Identical or different from 0,1, 2,3, 4,5 or 6; j is the same as ₂ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; j is the same as ₃ The same or different is selected from 0,1, 2,3 or 4; when two or more Ri's are present, the two or more Ri's are the same as or different from each other.

Preferably, said R is ₁₁ Any one selected from hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl and triphenylene; the R is ₁₁ May be substituted with one or more substituents which may be the same or different, 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, anthracenyl, phenanthrenyl, triphenylenyl; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

Preferably, the Ri are the same or different and are selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene; the Ri 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, anthracenyl, phenanthrenyl, triphenylenyl; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

Preferably, the carbazole-based derivative represented by formula 1 is selected from any one of the following structures,

preferably, the heterocyclic derivative represented by the formula 2 is selected from any one of the following structures,

preferably, A is selected from any one of the following structures,

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

v is ₁ The same or different is selected from 0,1, 2,3, 4,5 or 6; v is ₂ Identical or different from 0,1, 2,3, 4,5, 6,7 or 8; v is ₃ The same or different is selected from 0,1, 2,3, 4 or 5; when two or more Ra's are present, the sum of the two or more Ra' sAre the same or different from each other;

n is ₁ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; n is ₂ The same or different is selected from 0,1, 2,3, 4,5, 6,7, 8,9 or 10; n is said ₃ The same or different is selected from 0,1, 2,3, 4 or 5; n is said ₄ The same or different is selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11; n is ₅ Identical or different from 0,1, 2,3, 4,5, 6,7, 8 or 9; n is ₆ The same or different is selected from 0,1, 2,3 or 4; n is ₇ Identical or different from 0,1, 2,3, 4,5, 6 or 7; n is said ₈ The same or different is selected from 0,1, 2 or 3; n is ₉ The same or different is selected from 0,1, 2,3, 4,5 or 6; when two or more R's are present ₁₂ When two or more R are present ₁₂ 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 may be substituted by 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, anthracyl, phenanthryl, triphenylenyl; when two or more substituents are present, the two or more substituents may be the same as or different from each other.

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

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

In the present invention, at most one or at most two of the 4 x's per ring are selected from N, and the others are selected from CRc. More preferably, when there are two x selected from N, the two N are not adjacent.

In the present invention, of the 4 z's in each ring, at most one or at most two z's are selected from N, the others from CRa. More preferably, when there are two z selected from N, the two N are not adjacent.

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

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

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

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

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

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

Preferably, the

Any one selected from 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;

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

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

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

in the light-emitting layer 3 of the present invention, the weight ratio of the carbazole-based derivative represented by formula 1 to the heterocyclic-based derivative represented by formula 2 is 1.

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 thereof include, but are not limited to, complex compounds of transition metals, lanthanides, and actinides. Preferably, the doping material has a structure shown in formula 3 below:

m is selected from any one of Ir, pt, pd, au, rh, ru, os, re, cu, ag, ni, co, W and Eu;

l is selected from formula 3-1 or formula 3-2:

the R is ₁₀₀ To R ₁₀₃ Any one of the same or different 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 an adjacent substituent to form a substituted or unsubstituted ring;

the R is ₁₀₄ To R ₁₀₇ Any one of the same or different groups selected from 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 an adjacent substituent 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, and substituted or unsubstituted C1-C30 alkoxy; or R201 to R211 may be linked to an adjacent substituent to form a substituted or unsubstituted ring;

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 have 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 include a light emitting layer emitting light of a different color from each other or a light emitting layer emitting light of the same color. That is, the emission color may vary depending on the substance constituting the light emitting layer. For example, the plurality of light emitting layer stacks may include a substance emitting light of blue, green, red, yellow, white, or the like, and may be formed using a phosphorescent or fluorescent substance. At this time, the colors emitted by the light emitting layers may be complementary to each other. In addition, the color may be selected according to 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 including 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 including a hole blocking layer 9, an electron transport layer 10, and an electron injection layer 11, with respect to the light-emitting layer 3. 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 preferably uses 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, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalene-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (HNBphen), 8-hydroxyquinoline-Lithium (LiQ), and the like, but are not limited thereto.

In the organic electroluminescent device 100 according to the present invention, the electron transport layer 10 preferably uses a material having a strong 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, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalene-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (hnq), and the like, but are not limited thereto.

In the organic electroluminescent device 100 according to the present invention, the electron injection layer 11 is preferably made of a material having a small potential barrier with respect to an adjacent organic transport material and having an electron injection effect from the 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 metalsSalt (such as MgF) ₂ ) Metal oxides (e.g. Al) ₂ O ₃ 、MoO ₃ ) But is 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 facilitating 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, and the like, and alloys thereof; multilayer metallic materials, e.g. LiF/Al, mg/Ag, li/Al, liO ₂ /Al、BaF ₂ Al, etc., but are not limited thereto.

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

However, the structure of the organic electroluminescent device 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 the parameter requirements of the device and the characteristics of the material, may have additional or omitted organic layers, and may have a stacked structure with more than two organic layers having the same function.

The light emitting type of the organic electroluminescent device 100 according to the present invention may be a top emission device or a bottom emission device, and the difference between the top emission device and the bottom emission device is whether the light emitting direction of the device is emitted through the substrate or the light emitting direction deviates from the substrate. For bottom-emitting devices, the light-emitting direction of the device is through the substrate emission; for a top-emitting device, the light-emitting direction of the device is the direction away from the substrate.

The structure of the organic electroluminescent device 100 of the present invention may be a front-mounted structure or an inverted structure, and the difference between the two structures is that the organic layers are made in different orders, specifically: the positive structure is formed by sequentially forming a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, a hole transport layer, a hole injection layer and an anode on a substrate, and the negative structure is formed by sequentially forming an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode on a substrate.

The organic electroluminescent device 100 of the present invention may employ 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, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, sign board, signal lamp, etc.

The invention is explained in more detail by the following examples, without wishing to restrict the invention 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 inventive effort.

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

Preparation of formula 1:

preparation of formula 2:

description of raw materials, reagents and characterization equipment:

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

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

the element analysis was carried out using a Vario EL cube type organic element analyzer of Elementar, germany, and the sample mass was 5 to 10mg; synthesis of intermediates

Synthesis example 1 Synthesis of Compounds 1 to 5

Preparation of intermediate 1-5-A:

adding 1-5-a (100.00mmol, 27.94g), 1, 10-phenanthroline (20.00mmol, 3.60g) and anhydrous K into a reaction bottle under the protection of nitrogen ₃ PO ₄ (200.00mmol, 42.45g), 1-5-b (100.00mmol, 19.15g), DMSO (300.00 ml), cuI (20.00mmol, 3.81g), was stirred under heating and refluxed for 24 hours. After the reaction is finished, cooling the reaction liquid to room temperature, adding water for quenching, extracting by using chloroform, adding a small amount of activated carbon into an organic phase, heating and refluxing for 0.5 hour for decoloring, filtering, removing a solvent under reduced pressure, and then performing column chromatography, wherein the mobile phase is dichloromethane: petroleum ether (1The bulk purity is more than or equal to 99.73 percent.

Preparation of intermediate 1-5-B:

1-5-A (70.00mmol, 27.30g), 1-5-c (70.00mmol, 17.17g), sodium tert-butoxide (105.00mmol, 10.09g), toluene (250.00 mL), palladium acetate (0.70mmol, 0.16g) and tri-tert-butylphosphine (1.05mmol, 0.21g) were added to a reaction flask under nitrogen protection, and the mixture was dissolved by stirring and refluxed for 4.5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, water was added, extraction was performed with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, filtered, 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 purity of solid was 99.83% or more by HPLC.

Preparation of Compounds 1-5:

1-5-B (35.00mmol, 20.96g), 1-5-d (35.00mmol, 7.25g), sodium tert-butoxide (70.00mmol, 6.73g), toluene (250.00 mL), dibenzylideneacetone dipalladium (0.35mmol, 0.32g) and tri-tert-butylphosphine (0.70mmol, 0.14g) were added to a reaction flask under nitrogen protection, stirred and dissolved, and reacted for 7.5 hours under reflux. After 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, filtered, the solvent was removed under reduced pressure, and recrystallization was performed with toluene to obtain compound 1-5 (19.54 g, yield 77%) having a solid purity of 99.96% or more by HPLC. Mass spectrum m/z:724.3828 (theoretical value: 724.3817). Theoretical element content (%) C ₅₄ H ₄₈ N ₂ : c,89.46; h,6.67; and N,3.86. Measured elemental content (%): c,89.47; h,6.65; and N,3.88.

Synthesis example 2 Synthesis of Compounds 1 to 25

Preparation of intermediates 1-25-d:

under the protection of nitrogen, 1-25-e (70.00mmol, 17.95g), 1-25-f (70.00mmol, 14.49g) and Pd (PPh) are added into a reaction bottle ₃ ) ₄ (1.40mmol，1.62g)、K ₂ CO ₃ (140.00mmol, 19.35g) and 300mL of toluene, 100mL of ethanol, 100mL of water,stirring the mixture, and heating and refluxing the reactant system for reaction for 2.5 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally performing filtration on the filter cake with a toluene/ethanol =4:1 recrystallization to give 1-25-d (18.97 g, 80% yield); the purity of the solid is more than or equal to 99.21 percent by HPLC detection. Mass spectrum m/z:338.0851 (theoretical value: 338.0862).

Preparation of Compounds 1-25:

according to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-25-a,1-5-b with equimolar 1-25-b,1-5-c with equimolar 1-25-c, and 1-5-d with equimolar 1-25-d to give 1-25 (19.76 g, 74% yield), and the solid purity by HPLC was 99.97% or more. Mass spectrum m/z:762.3047 (theoretical value: 762.3035). Theoretical element content (%) C ₅₈ H ₃₈ N ₂ : c,91.31; h,5.02; n,3.67. Measured elemental content (%): c,91.33; h,5.01; and N,3.69.

Synthesis example 3 Synthesis of Compounds 1 to 69

According to the preparation 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 solid purity by HPLC analysis was 99.95% or more. Mass spectrum m/z:709.3485 (theoretical value: 709.3474). Theoretical element content (%) C ₅₃ H ₃₁ D ₇ N ₂ : c,89.67; h,6.39; and N,3.95. Measured elemental content (%): c,89.69; h,6.38; and N,3.97.

Synthesis example 4 Synthesis of Compounds 1 to 131

According to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b with equimolar 1-131-b, and 1-5-c with equimolar1-131-c,1-5-d was replaced with equimolar 1-131-d to give 1-131 (18.29 g) with a solid purity of 99.97% or more by HPLC. Mass spectrum m/z:696.3395 (theoretical value: 696.3381). Theoretical element content (%) C ₅₂ H ₂₈ D ₈ N ₂ : c,89.62; h,6.36; and N,4.02. Measured elemental content (%): c,89.63; h,6.33; and N,4.05.

Synthesis example 5 Synthesis of Compounds 1 to 151

According to the preparation 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 1-25-c, and 1-5-d was replaced with equimolar 1-151-d to give 1-151 (18.81 g) with a solid purity of 99.98% or more as measured by HPLC. Mass spectrum m/z:688.2888 (theoretical value: 688.2878). Theoretical element content (%) C ₅₂ H ₃₆ N ₂ : c,90.67; h,5.27; and N,4.07. Measured elemental content (%): c,90.69; h,5.28; and N,4.05.

Synthesis example 6 Synthesis of Compounds 1 to 153

According to the preparation 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 solid purity by HPLC was 99.96% or more. Mass spectrum m/z:928.3830 (theoretical value: 928.3817). Theoretical element content (%) C ₇₁ H ₄₈ N ₂ : c,91.78; h,5.21; and N,3.01. Measured elemental content (%): c,91.77; h,5.23; and N,3.03.

Synthesis example 7 Synthesis of Compounds 1 to 155

According to the preparation 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 solid purity by HPLC was 99.95% or more. Mass spectrum m/z:778.2424 (theoretical value: 778.2407). Theoretical element content (%) C ₅₂ H ₃₁ F ₅ N ₂ : c,80.19; h,4.01; and N,3.60. Measured elemental content (%): c,80.18; h,4.03; and N,3.63.

Synthesis example 8 Synthesis of Compounds 1 to 171

According to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-171-a,1-5-b with equimolar 1-171-b,1-5-c with equimolar 1-171-c, and 1-5-d with equimolar 1-171-d to give 1-171 (20.20 g) and the solid purity by HPLC was 99.96% or more. Mass spectrum m/z:812.2951 (theoretical value: 812.2940). Theoretical element content (%) C ₆₀ H ₃₆ N ₄ : c,88.64; h,4.46; and N,6.89. Measured elemental content (%): c,88.65; h,4.47; and N,6.86.

Synthesis example 9 Synthesis of Compounds 1 to 203

According to the preparation 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) with a solid purity of 99.98% or more by HPLC. Mass spectrum m/z:742.3296 (theoretical value: 742.3286). Theoretical element content (%) C ₅₆ H ₃₄ D ₄ N ₂ : c,90.53; h,5.70; n,3.77. Measured elemental content (%): c,90.51; h,5.72; n,3.78.

Synthesis example 10 Synthesis of Compounds 1 to 223

According to the preparation 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 1-223-c, and 1-5-d was replaced with equimolar 1-171-d to give 1-223 (24.86 g) with a solid purity of 99.97% or more by HPLC. Mass spectrum m/z:1028.4119 (theoretical value: 1028.4130). Theoretical element content (%) C ₇₉ H ₅₂ N ₂ : c,92.19; h,5.09; and N,2.72. Measured elemental content (%): c,92.18; h,5.08; and N,2.75.

Synthesis example 11 Synthesis of Compounds 1 to 271

According to the preparation 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 solid purity by HPLC analysis was 99.95% or more. Mass spectrum m/z:778.3333 (theoretical value: 778.3348). Theoretical element content (%) C ₅₉ H ₄₂ N ₂ : c,90.97; h,5.43; and N,3.60. Measured elemental content (%): c,90.95; h,5.47; and N,3.63.

Synthesis example 12 Synthesis of Compounds 1 to 272

According to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b with equimolar 1-272-b,1-5-c with equimolar 1-203-c, and 1-5-d with equimolar 1-151-d to give 1-272 (20.92 g), and the solid purity by HPLC was 99.98% or more. Mass spectrum m/z:746.3550 (theoretical value: 746.3537). Theoretical element content (%) C ₅₆ H ₃₀ D ₈ N ₂ : c,90.04; h,6.21; and N,3.75. Measured elemental content (%): c,90.05; h,6.23; n,3.73.

Synthesis example 13 Synthesis of Compounds 1 to 288

According to the preparation 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) with a solid purity of 99.97% or more by HPLC. Mass spectrum m/z:924.3112 (theoretical value: 924.3128). Theoretical element content (%) C ₆₅ H ₄₀ F ₄ N ₂ : c,84.40; h,4.36; and N,3.03. Measured elemental content (%): c,84.38; h,4.38; and N,3.02.

Synthesis example 14 Synthesis of Compounds 1 to 295

According to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b with equimolar 1-151-b,1-5-c with equimolar 1-295-c, and 1-5-d with equimolar 1-295-d to give 1-295 (22.76 g), and the solid purity by HPLC was 99.95% or more. Mass spectrum m/z:928.3830 (theoretical value: 928.3817). Theoretical element content (%) C ₇₁ H ₄₈ N ₂ : c,91.78; h,5.21; and N,3.01. Measured elemental content (%): c,91.77; h,5.20; and N,3.08.

Synthesis example 15 Synthesis of Compounds 1 to 301

According to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b with equimolar 1-151-b,1-5-cEquimolar 1-301-c,1-5-d was replaced with equimolar 1-151-d to give 1-301 (24.95 g), with a solid purity of 99.96% or more as determined by HPLC. Mass spectrum m/z:962.4614 (theoretical value: 962.4600). Theoretical element content (%) C ₇₃ H ₅₈ N ₂ : c,91.02; h,6.07; and N,2.91. Measured elemental content (%): c,91.03; h,6.08; and N,2.85.

Synthesis example 16 Synthesis of Compounds 1 to 309

According to the preparation method in 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) with a solid purity of 99.97% or more by HPLC. Mass spectrum m/z:721.3326 (theoretical value: 721.3333). Theoretical element content (%) C ₅₃ H ₂₇ D ₈ N ₃ : c,88.18; h,6.00; n,5.82. Measured elemental content (%): c,88.16; h,6.03; and N,5.85.

Synthesis example 17 Synthesis of Compounds 1 to 317

According to the preparation 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) with a solid purity of 99.98% or more by HPLC. Mass spectrum m/z:774.3982 (theoretical value: 774.3974). Theoretical element content (%) C ₅₈ H ₅₀ N ₂ : c,89.88; h,6.50; and N,3.61. Measured elemental content (%): c,89.87; h,6.51; and N,3.63.

Synthesis example 18 Synthesis of Compounds 1 to 344

According to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-69-a,1-5-b was replaced with equimolar 1-344-b, and 1-5-c was replaced with equimolar 1-344-c to give 1-344 (20.85 g), which was determined to have a solid purity of 99.97% or more by HPLC. Mass spectrum m/z:850.3330 (theoretical value: 850.3348). Theoretical element content (%) C ₆₅ H ₄₂ N ₂ : c,91.73; h,4.97; and N,3.29. Measured elemental content (%): c,91.74; h,4.95; and N,3.28.

Synthesis example 19 Synthesis of Compounds 1-392

According to the preparation method in Synthesis example 2, 1-392-e was replaced with 1-392-e in equimolar amount, 1-25-f was replaced with 1-392-f in equimolar amount, 1-25-a was replaced with 1-69-a in equimolar amount, 1-25-b was replaced with 1-344-b in equimolar amount, 1-25-c was replaced with 1-392-c in equimolar amount, and 1-25-d was replaced with 1-392-d in equimolar amount, to give 1-392 (21.92 g), and the solid purity was 99.95% or more by HPLC. Mass spectrum m/z:920.4028 (theoretical value: 920.4038). Theoretical element content (%) C ₇₀ H ₄₀ D ₆ N ₂ : c,91.27; h,5.69; and N,3.04. Measured elemental content (%): c,91.28; h,5.68; and N,3.08.

Synthesis example 20 Synthesis of Compounds 1 to 424

According to the preparation method in Synthesis example 1, 1-5-a was replaced with equimolar 1-424-a,1-5-b with equimolar 1-424-b,1-5-c with equimolar 1-424-c, and 1-5-d with equimolar 1-424-d to give 1-424 (22.17 g), and the solid purity by HPLC was 99.98% or more. Mass spectrum m/z:855.3484 (theoretical value: 855.3473). Theoretical element content (%) C ₆₂ H ₃₅ D ₅ F ₂ N ₂ : c,86.99; h,5.30; and N,3.27. Measured elemental content (%): c,86.97; h,5.28；N,3.28。

Preparation of intermediate 2-1-B

Synthesis of intermediate 2-1-A

Under the protection of nitrogen, 2-1-a (24.66g, 120.00mmol), pinacol diboron (30.47g, 120.00mmol) and Pd (PPh) are added into a reaction bottle ₃ ) ₄ (2.31g，2.00mmol)、K ₂ CO ₃ (24.88g, 180.00mmol) and DMF (500.00 mL) are heated to react for 2.5 hours, after the reaction is finished, distilled water is added, dichloromethane is used for extraction, liquid separation is carried out, the organic phase is washed three times by distilled water, anhydrous magnesium sulfate is used for drying, the solvent is concentrated by rotary evaporation, the temperature is reduced, crystallization is carried out, suction filtration is 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 more than or equal to 98.81 percent. Mass spectrum m/z:252.1072 (theoretical value: 252.1088).

Synthesis of intermediate 2-1-B

Under the protection of nitrogen, the intermediate 2-1-A (22.73g, 90.00mmol), the raw material 2-1-b (25.46g, 90.00mmol) and K are added into a reaction bottle in sequence ₂ CO ₃ (19.35g，140.00mmol)、Pd(PPh ₃ ) ₄ (1.16g, 1.00mmol), 400mL of a toluene/ethanol/water (2. After the reaction is finished, cooling to room temperature, adding methylbenzene to separate phases, washing the methylbenzene phase with distilled water for three times, drying with anhydrous magnesium sulfate, carrying out rotary evaporation to concentrate a solvent, cooling to crystallize, carrying out suction filtration, and adding toluene to the obtained solid: ethanol =20:3 recrystallization to give intermediate 2-1-B (20.27 g, yield 80%). The HPLC purity is more than or equal to 99.83 percent. Mass spectrum m/z:279.9667 (theoretical value: 279.9654).

The following intermediates were synthesized according to the above procedure by equimolar replacement of starting material 2-1-a and starting material 2-1-b:

synthesis example 21 Synthesis of Compound 2-1

Preparation of intermediate 2-1-C:

under the protection of nitrogen, raw materials 2-1-c (39.73g, 100.00mmol), pinacol diboron (25.39g, 100.00mmol) and Pd (PPh) are sequentially added into a reaction bottle ₃ ) ₄ (1.73g，1.50mmol)、K ₂ CO ₃ (30.41g, 220.00mmol), DMF (400.00 mL), then heated to react for 4 hours, after the reaction was complete, cooled to room temperature, 500.00mL of water was added thereto, followed by extraction with ethyl acetate (500.00 mL. Times.3), the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed by rotary evaporation, and then the reaction mixture was cooled with toluene: ethanol =20:1 to obtain an intermediate 2-1-C (37.77 g, yield 85 percent) through recrystallization and drying; HPLC purity is more than or equal to 98.70 percent. Mass spectrum m/z:444.2275 (theoretical value: 444.2261).

Preparation of intermediate 2-1-D:

under the protection of nitrogen, the intermediate 2-1-C (31.11g, 70.00mmol), the raw material 2-1-B (19.71g, 70.00mmol) and Pd (PPh) are added into a reaction bottle in sequence ₃ ) ₄ (1.39g，1.20mmol)、K ₂ CO ₃ (13.82g, 100.00mmol) and 300.00mL of toluene, 100mL of ethanol and 100mL of water, stirring the mixture, and heating the system under reflux for 3.5 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration to obtain a filter cake, washing 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%); the HPLC purity is more than or equal to 99.45 percent. Mass spectrum m/z:518.1818 (theoretical value: 518.1801).

Preparation of intermediate 2-1-E:

under the protection of nitrogen, the intermediate 21-D (25.95g, 50.00mmol) and the pinacol ester diboron (12) are added in sequence to a reaction flask.70g，50.00mmol)，KOAc(10.80g，110.00mmol)，Pd(dppf)Cl ₂ (0.73g, 1.00mmol), 1, 4-dioxane (350.00 mL), then heated to reflux temperature for 4.5 hours, after the reaction was completed, cooled to room temperature, 350.00mL of water was added thereto, then extracted with ethyl acetate (500.00 mL. Times.3), and the organic layer was over anhydrous MgSO ₄ Drying, removing ethyl acetate by rotary evaporation, then recrystallizing by using toluene, and drying to obtain an intermediate 2-1-E (24.12 g, yield 79%); the HPLC purity is more than or equal to 99.83 percent. Mass spectrum m/z:610.3033 (theoretical value: 610.3043).

Preparation of Compound 2-1:

under the protection of nitrogen, the intermediate 2-1-E (18.32g, 30.00mmol), the raw material 2-1-d (5.94g, 30.00mmol) and Pd were sequentially added into a reaction flask ₂ (dba) ₃ (0.46g，0.50mmol)、P(t-Bu) ₃ (0.30g，1.50mmol)，K ₂ CO ₃ (6.91g, 50.00mmol) and 150.00mL of tetrahydrofuran, the mixture was stirred and the reactant system was heated to reflux for 5 hours; after the reaction was completed, cooling to room temperature, adding water, extracting with dichloromethane, drying the organic layer with anhydrous magnesium sulfate, filtering, removing the solvent under reduced pressure, and recrystallizing with toluene to obtain compound 2-1 (13.90 g, yield 77%); the HPLC purity is more than or equal to 99.95 percent. Mass spectrum m/z:601.2418 (theoretical value: 601.2406). Theoretical element content (%) C ₄₅ H ₃₁ NO: c,89.82; h,5.19; n,2.33. Measured elemental content (%): c,89.85; h,5.15; and N,2.36.

Synthesis example 22 Synthesis of Compounds 2 to 35

Using the same method as in example 21, compound 2-35 (11.42 g) was synthesized by substituting 2-1-c with 2-35-c in an equimolar amount and 2-1-B with 2-35-B in an equimolar amount, and its solid purity was ≧ 99.96% by HPLC. Mass spectrum m/z:507.2370 (theoretical value: 507.2359). Theoretical element content (%) C ₃₆ H ₂₁ D ₅ N ₂ O: c,85.18; h,6.15; n,5.52. Measured elemental 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, compound 2-106 (14.22 g) was synthesized by substituting 2-1-B with 2-106-B in an equimolar amount and substituting 2-1-d with 2-106-d in an equimolar amount, 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 ₄₆ H ₃₃ NO: c,89.73; h,5.40; and N,2.27. Measured elemental content (%): c,89.75; h,5.43; and N,2.23.

Synthesis example 24 Synthesis of Compounds 2 to 123

Compound 2-123 (16.74 g) was synthesized by the same method as in example 21 except that 2-1-c was replaced with an equal mole of 2-123-c and 2-1-B was replaced with an equal mole of 2-123-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 ₅₀ H ₃₇ F ₄ NO: c,80.74; h,5.01; n,1.88. Measured elemental content (%): c,80.75; h,5.02; n,1.85.

Synthesis example 25 Synthesis of Compounds 2 to 162

Compound 2-162 (14.77 g) was synthesized in the same manner as in example 21 except for using 2-162-B in place of 2-1-B in an equimolar amount, and purity by HPLC was ≧ 99.97%. Mass spectrum m/z:647.3138 (theoretical value: 647.3126). Theoretical element content (%) C ₄₈ H ₃₃ D ₄ NO: c,88.99; h,6.38; and N,2.16. Measured elemental content (%): c,88.95; h,6.41; and N,2.18.

[ Synthesis example 26] Synthesis of Compounds 2 to 287

The same procedure as in example 21 was used, substituting 2-1-B with an equimolar amount of 2-287-B and substituting 2-1-d with an equimolar amount of 2-287-d. Compound 2-287 (16.16 g) was synthesized with a solid purity ≧ 99.96% by HPLC. Mass spectrum m/z:727.2883 (theoretical value: 727.2875). Theoretical element content (%) C ₅₅ H ₃₇ NO: c,90.75; h,5.12; n,1.92. Measured elemental content (%): c,90.72; h,5.16; and N,1.95.

Synthesis example 27 Synthesis of Compounds 2-326

The same procedure as in example 21 was used, substituting equimolar 2-326-c for 2-1-c and equimolar 2-326-B for 2-1-B. Compound 2-326 (11.60 g) was synthesized with a purity of 99.95% or more as determined by HPLC. Mass spectrum m/z:495.2518 (theoretical value: 495.2500). Theoretical element content (%) C ₃₆ H ₂₅ D ₄ NO: c,87.24; h,6.71; n,2.83. Measured elemental content (%): c,87.23; h,6.73; and N,2.85.

Synthesis example 28 Synthesis of Compounds 2 to 341

The same procedure as in example 21 was used, substituting equimolar 2-341-c for 2-1-c, equimolar 2-341-B for 2-1-B, and equimolar 2-341-d for 2-1-d. Compound 2-341 (16.37 g) was synthesized with a solid purity of 99.94% or more by HPLC. Mass spectrum m/z:757.4233 (theoretical value: 757.4222). Theoretical element content (%) C ₅₆ H ₄₇ D ₄ NO: c,88.73; h,7.31; n,1.85. Measured elemental content (%): c,88.75; h,7.33; n,1.83.

Synthesis example 29 Synthesis of Compounds 2 to 377

Using the same procedure 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, and the purity of the solid was ≧ 99.97% by HPLC. Mass spectrum m/z:641.2118 (theoretical value: 641.2103). Theoretical element content (%) C ₄₅ H ₂₇ N ₃ O ₂ : c,84.22; h,4.24; and N,6.55. Measured elemental content (%): c,84.23; h,4.23; n,6.51.

Synthesis example 30 Synthesis of Compounds 2 to 394

In the same manner 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, and the purity of the solid was ≧ 99.96% by HPLC. Mass spectrum m/z:591.2551 (theoretical value: 591.2562). Theoretical element content (%) C ₄₄ H ₃₃ NO: c,89.31; h,5.62; n,2.37. Measured elemental content (%): c,89.28; h,5.63; and N,2.38.

Synthesis example 31 Synthesis of Compounds 2 to 415

The same procedure as in example 21 was used, replacing 2-1-c with equimolar 2-415-c, replacing 2-1-B with equimolar 2-415-B, and replacing 2-1-d 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 ₅₃ H ₅₁ NO: c,88.66; h,7.16; and N,1.95. Measured elemental content (%): c,88.65; h,7.18; and N,1.91.

Synthesis example 32 Synthesis of Compounds 2-474

The same procedure as in example 21 was used, replacing 2-1-c with equimolar 2-474-c, replacing 2-1-B with equimolar 2-474-B and replacing 2-1-d 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 ₅₀ H ₃₄ N ₂ S: c,86.42; h,4.93; and N,4.03. Measured elemental content (%): c,86.43; h,4.95; and N,4.02.

Synthesis example 33 Synthesis of Compounds 2 to 505

In the same manner 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 with a solid purity of 99.96% or more by HPLC. Mass spectrum m/z:699.2572 (theoretical value: 699.2562). Theoretical element content (%) C ₅₃ H ₃₃ NO: c,90.96; h,4.75; n,2.00. Measured elemental content (%): c,90.95; h,4.72; and N,2.03.

Synthesis example 34 Synthesis of Compounds 2 to 518

The same procedure as in example 21 was used, substituting equimolar 2-518-c for 2-1-c, equimolar 2-518-B for 2-1-B, and equimolar 2-518-d for 2-1-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 ₄₉ H ₄₀ N ₂ S: c,85.43; h,5.85; and N,4.07. Measured elemental content(％)：C,85.42；H,5.88；N,4.08。

Synthesis example 35 Synthesis of Compound 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, and the purity of the solid was ≧ 99.97% by HPLC. Mass spectrum m/z:719.3195 (theoretical value: 719.3188). Theoretical element content (%) C ₅₄ H ₄₁ NO: c,90.09; h,5.74; and N,1.95. Measured elemental content (%): c,90.08; h,5.72; and N,1.96.

Synthesis example 36 Synthesis of Compounds 2 to 550

The same procedure as in example 21 was used, substituting equimolar 2-550-c for 2-1-c, equimolar 2-550-B for 2-1-B, and equimolar 2-550-d for 2-1-d. Compound 2-550 (13.56 g) was synthesized with a solid purity of 99.96% or more by HPLC. Mass spectrum m/z:664.2891 (theoretical value: 664.2878). Theoretical element content (%) C ₅₀ H ₃₆ N ₂ : c,90.33; h,5.46; n,4.21. Measured elemental content (%): c,90.28; h,5.47; and N,4.23.

[ Synthesis example 37] Synthesis of Compound 2-586

The same procedure as in example 21 was used, replacing 2-1-c with equimolar 2-586-c, replacing 2-1-B with equimolar 2-586-B, and replacing 2-1-d with equimolar 2-586-d. Compound 2-586 (14.40 g) was synthesized, and purity of the solid was ≧ 99.95% by HPLC. Mass spectrum m/z:695.3138 (theoretical value: 695.3128). Theoretical element content (%) C ₅₀ H ₃₃ D ₃ N ₄ ：C,86.30(ii) a H,5.65; and N,8.05. Measured elemental content (%): c,86.28; h,5.66; and N,8.07.

Synthesis example 38 Synthesis of Compounds 2 to 604

The same procedure as in example 21 was used, substituting equimolar 2-604-c for 2-1-c, equimolar 2-604-B for 2-1-B, and equimolar 2-604-d for 2-1-d. Compound 2-604 (12.26 g) was synthesized, and the purity of the solid was ≧ 99.97% by HPLC. Mass spectrum m/z:575.2569 (theoretical value: 575.2554). Theoretical element content (%) C ₄₁ H ₂₅ D ₆ And NS: c,85.52; h,6.48; and N,2.43. Measured elemental content (%): c,85.51; h,6.47; and N,2.47.

[ Synthesis example 39] Synthesis of Compound 2-629

The same procedure as in example 21 was used, substituting 2-1-c with an equimolar amount of 2-629-c, substituting 2-1-B with an equimolar amount of 2-629-B, and substituting 2-1-d with an equimolar amount of 2-629-d. Compound 2-629 (12.49 g) was synthesized, and the purity of the solid was ≧ 99.98% by HPLC. Mass spectrum m/z:594.1885 (theoretical value: 594.1878). Theoretical element content (%) C ₄₀ H ₂₆ N ₄ S: c,80.78; h,4.41; and N,9.42. Measured elemental content (%): c,80.77; h,4.43; and N,9.45.

Synthesis example 40 Synthesis of Compounds 2-661

The same procedure as in example 21 was used, substituting equimolar 2-505-c for 2-1-c, equimolar 2-661-B for 2-1-B, and equimolar 2-106-d for 2-1-d. Compound 2-661 (15.49 g) was synthesized with a solid purity ≧ 99.97% by HPLC. Mass spectrum m/z:7.3358 (theoretical value: 697.3345). Theory of thingsArgument content (%) C ₅₂ H ₄₃ NO: c,89.49; h,6.21; and N,2.01. Measured elemental content (%): c,89.47; h,6.23; and N,2.03.

Device examples 1 to 20

The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then is ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropyl acetone for 20 min, and drying at 120 deg.C. Vacuum evaporating HI on the ITO substrate to form an evaporated layer with the thickness of 15nm as a hole injection layer; evaporating HT on the hole injection layer in vacuum to be used as a hole transmission layer, wherein the evaporation thickness is 80nm; a mixture of compounds 1 to 5 (first host) of the present invention and compounds 2 to 586 (second host) of the present invention at a weight ratio of 5: dopant D-18=92 (mass ratio) as a light-emitting layer, and the vapor deposition thickness was 20nm; vacuum evaporation of ET on the light emitting layer is used as an electron transport layer, and the evaporation thickness is 30nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70nm.

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

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

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

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

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

Table 1 test of light emitting characteristics of organic electroluminescent device

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

Device examples 21 to 40

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

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

Comparative example 27: the ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then is ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. Vacuum evaporating HI on the ITO substrate to form an evaporated layer with the thickness of 15nm as a hole injection layer; evaporating HT on the hole injection layer in vacuum to be used as a hole transmission layer, wherein the evaporation thickness is 80nm; vacuum evaporation of compounds 1 to 5 of the invention on the hole transport layer: dopant D-18=95 (mass ratio) as a light-emitting layer, and the vapor deposition thickness was 20nm; vacuum evaporation of ET on the light emitting layer is used as an electron transport layer, and the evaporation thickness is 30nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70nm.

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

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

Table 2 test of light emitting characteristics of organic electroluminescent device

As can be seen from the results in Table 2, the devices of examples 21 to 40 exhibited higher luminous efficiency and longer device life than those of comparative examples 27 to 48. The two materials are combined to ensure that the carrier transmission in the luminescent layer is balanced, and the recombination probability of excitons in the luminescent layer is greatly improved, so that the organic electroluminescent device can be used as a luminescent layer main body material in the organic electroluminescent device, the luminescent efficiency of the device can be improved, and the service life of the device can be effectively prolonged.

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

Claims

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

in the formula 1, L ₁ Selected from any one of the structures shown below,

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

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

the R is ₆ 、R ₇ 、R ₈ Any one of the same or different 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 is ₆ 、R ₇ May be linked to form a substituted or unsubstituted ring;

said L ₄ Selected from any one of the structures shown below,

wherein at least one R ₉ 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 of R ₉ Any one of hydrogen, deuterium, halogen and cyano, which are the same or different;

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

said X ₁ Any one selected from O, S and NRb;

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

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

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

3. An organic electroluminescent device according to claim 1, wherein L is ₂ 、L ₃ The same or different is selected from a single bond or any one of the structures shown below,

the R is ₁₁ Ri 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;

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

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

4. An organic electroluminescent device according to claim 1, wherein the organic electroluminescent device is characterized in that

Selected from any one of the structures shown below,

5. the organic electroluminescent device according to claim 1, wherein the carbazole-based derivative represented by formula 1 is selected from any one of the following structures,

6. the organic electroluminescent device of claim 1, wherein the heterocyclic derivative represented by formula 2 is selected from any one of the following structures,

7. the organic electroluminescent device of claim 1, wherein A is selected from any one of the following structures,

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

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

8. An organic electroluminescent device according to claim 1, wherein L is L ₄ The same or different is selected from any one of the structures shown below,

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

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

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

said e ₁ The same or different is selected from 0,1, 2,3 or 4; said e ₂ Identical or different from 0,1, 2,3, 4,5 or 6; said e ₃ The same or different is selected from 0,1 or 2; said e ₄ Identical or different from 0,1, 2 or 3; when two or more R9 groups are present, two or more R groups ₉ Are the same or different from each other; when two or more R's are present ₉ When, two or more R ₉ ' may be the same or different from each other;

said p is ₁ The same or different is selected from 0,1, 2,3, 4,5, 6,7 or 8; said p is ₂ Identical or different from 0,1, 2,3, 4,5 or 6; said p is ₃ The same or different is selected from 0,1, 2,3 or 4; said p is ₄ The same or different is selected from 0,1 or 2; said p is ₅ The same or different is selected from 0,1, 2,3, 4,5, 6,7, 8,9 or 10; when two or more R's are present ₁₃ When two or more R are present ₁₃ The same or different from each other.

9. An organic electroluminescent device according to claim 1, wherein the organic electroluminescent device is characterized in that

Selected from any one of the structures shown below,

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

the R is ₄ The same or different ones are selected from hydrogen, deuterium, cyano-group, halogen, substituted or unsubstituted C1-C12 alkyl, and substituted or unsubstituted C6-C18 aryl.

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