CN117903091A

CN117903091A - Aromatic amine derivative and organic electroluminescent device thereof

Info

Publication number: CN117903091A
Application number: CN202410050384.1A
Authority: CN
Inventors: 董秀芹; 周雯庭; 韩春雪
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2024-01-12
Filing date: 2024-01-12
Publication date: 2024-04-19

Abstract

The invention provides an aromatic amine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. The aromatic amine derivative has excellent hole transmission capability, improves the luminous efficiency and the service life of the organic electroluminescent device when being applied to a hole transmission region in the organic electroluminescent device, has proper HOMO energy level, can be better matched with an adjacent functional layer, and has good application prospect when being applied to a P-type charge generation layer of the organic electroluminescent device, so that the luminous efficiency and the service life of the organic electroluminescent device are improved.

Description

Aromatic amine derivative and organic electroluminescent device thereof

Technical Field

The invention relates to the technical field of organic electroluminescent materials, in particular to an aromatic amine derivative and an organic electroluminescent device thereof.

Background

Organic Light-Emitting Diode (OLED) is also called an Organic Light-Emitting Diode (OLED), and is popular with more and more consumers as a new generation of display technology by virtue of its wide viewing angle, low energy consumption, fast response speed, and the like. Over decades, OLED technology has been successfully used in mobile phone screens, televisions, wearable devices, and other electronic devices. Although important developments and applications have been made in the related art, how to increase device lifetime and reduce device efficiency roll-off remains a hotspot in constant research in academia and industry.

Classical OLED device structures mainly include an anode, a cathode, a hole transport layer (Hole Transport Layer, HTL), an electron transport layer (Electron Transport Layer, ETL), and an emission layer (EML). Wherein, the common anode is transparent Indium Tin Oxide (ITO) material, the cathode is low-power consumption metal aluminum, and HTL, ETL, EML is organic semiconductor material. In order to obtain better device effects, organic semiconductor materials such as an electron injection layer (Electron Inject Layer, EIL), a hole injection layer (Hole Injection Layer, HIL), an electron blocking layer (Electron Blocking Layer, EBL), and a hole blocking layer (Hole Blocking Layer, HBL) are also introduced into the device structure. The OLED device operates according to the principle that when an external voltage is applied to the device, holes and electrons are injected from an anode and a cathode respectively, the holes and electrons migrate to the cathode and the anode through a transport layer under the action of an external electric field respectively, and are combined to form excitons after the light emitting layers are combined, and the excitons decay back to a ground state and emit photons through a series of photophysical processes, thereby generating a light emitting phenomenon.

The hole transport material is an important member of the OLED universal material, and the excellent performance of the hole transport material can improve the transport rate of holes in the device, so that the hole transport rate and the electron transport rate are balanced, and the holes and the electrons can be effectively matched in the light-emitting layer. In addition, the hole transport material with excellent performance can reduce energy barrier in the hole injection process, so that the hole injection efficiency is improved, and the efficiency, the service life and the brightness of the device are improved. Meanwhile, in order to solve the problems of service life and efficiency, a plurality of layers of hole transport layers with proper energy levels are generally added between the hole transport layers and the light-emitting layers, so that potential barriers between the hole transport layers and the light-emitting layers can be reduced, driving voltage of the organic electroluminescent device is reduced, utilization rate of holes is further increased, and light-emitting efficiency and service life of the device are improved. However, most of the existing hole transport materials have the problems of low hole mobility, poor film forming property, poor thermal stability and the like.

In order to further improve the current efficiency of the OLED and obtain a higher lifetime, a stacked organic electroluminescent device in which a plurality of light emitting units are electrically connected through a charge generation layer has become one of research hotspots. Under the external electric field, electrons and holes generated by the charge generation layer are respectively injected into adjacent light emitting units, and are combined in the light emitting units to form exciton luminescence. Therefore, the selection and design of the charge generation layer material is a key factor affecting the luminous efficiency and lifetime of the stacked organic electroluminescent device.

In view of the above problems, the development of a hole transport material having a high hole mobility and a suitable HOMO level and a material usable for the charge generation layer has become an important point of current research.

Disclosure of Invention

The invention aims to provide an aromatic amine derivative and an organic electroluminescent device thereof, which can develop an organic electroluminescent device with high efficiency and long service life when being applied to a hole transport layer or a P-type charge generation layer of the organic electroluminescent device, solve the problems of low luminous efficiency, short service life and the like of the organic electroluminescent device in the prior art, have a general formula shown in a structural formula 1,

Wherein R ₁ is selected from any one of a substituted or unsubstituted C1-C15 alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C15 alicyclic group, a substituted or unsubstituted C3-C15 condensed ring group of an alicyclic ring and a C6-C30 aromatic ring, and a substituted or unsubstituted C2-C30 heteroaryl group; r ₂ is selected from any one of substituted or unsubstituted aryl of C6-C30, fused ring group of substituted or unsubstituted alicyclic ring of C3-C15 and aromatic ring of C6-C30, and substituted or unsubstituted heteroaryl of C2-C30;

The R ₅、R₆ is independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted silyl;

Each occurrence of R ₃、R₄、R₇、R₈ is the same or different and is selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring, substituted or unsubstituted C2-C30 heteroaryl; or the adjacent two R ₃, the adjacent two R ₄, the adjacent two R ₇ and the adjacent two R ₈ are connected with each other to form a substituted or unsubstituted ring; said a is selected from 1,2, 3 or 4; said b is selected from 1,2, 3 or 4; said c is selected from 1,2, 3 or 4; said d is selected from 1,2, 3 or 4;

the X is selected from O atoms and N (R _d);

The v is, for each occurrence, identically or differently selected from N or CH; v at the bond is selected from C;

The R _d is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring group, substituted or unsubstituted C2-C30 heteroaryl;

each occurrence of said R _a、R_b、R_c is identically or differently selected from hydrogen or deuterium; said e is selected from 1, 2 or 3;

The L ₁、L₂ is independently selected from a single bond or a group as shown below:

the X ₁ is selected, identically or differently, from the group consisting of O atom, S atom, C (R _jR_k)、N(R_p) for each occurrence;

The X ₂ is selected, identically or differently, from the group consisting of O atom, S atom, N (R _q) for each occurrence;

The x is, for each occurrence, identically or differently selected from N or CH; x at the bond is selected from C;

The n is selected identically or differently from 1,2, 3, 4 or 5 for each occurrence;

the ring A is selected identically or differently from a substituted or unsubstituted C3 to C10 cycloaliphatic radical for each occurrence;

Each occurrence of R ₁₁ is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring, substituted or unsubstituted C2-C30 heteroaryl;

each occurrence of R _j、R_k is the same or different and is selected from any one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring group and substituted or unsubstituted C2-C30 heteroaryl group;

Each occurrence of R _p、R_q is the same or different and is selected from any one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring group and substituted or unsubstituted C2-C30 heteroaryl group;

Said g ₁ is selected, identically or differently, from 1, 2, 3, or 4 for each occurrence; said g ₂ is selected identically or differently from 1, 2, or 3 for each occurrence; said g ₃ is selected identically or differently from 1 or 2 for each occurrence;

The L ₃ is selected from a single bond or a group as shown below:

The Y ₁, at each occurrence, is identically or differently selected from O atoms, S atoms, C (R _mR_n)、N(R_t);

The Y ₂, at each occurrence, is identically or differently selected from O atoms, S atoms, N (R _s);

The z is, identically or differently, selected from N or CH for each occurrence; z at the bond is selected from C;

the m is selected identically or differently for each occurrence from 1,2, 3, 4 or 5;

The ring B is selected identically or differently from a substituted or unsubstituted C3 to C7 cycloaliphatic radical for each occurrence;

Each occurrence of R ₁₂ is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring, substituted or unsubstituted C2-C30 heteroaryl;

Each occurrence of R _m、R_n is the same or different and is selected from any one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring group and substituted or unsubstituted C2-C30 heteroaryl group; or the R _m and R _n are linked to each other to form a substituted or unsubstituted ring;

Each occurrence of R _t、R_s is the same or different and is selected from any one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring group and substituted or unsubstituted C2-C30 heteroaryl group;

Each occurrence of said h ₁ is identically or differently selected from 1, 2, 3, or 4; each occurrence of said h ₂ is identically or differently selected from 1, 2, or 3; the h ₃ is selected identically or differently from 1 or 2 for each occurrence.

The invention also provides an organic electroluminescent device, comprising: a first electrode; a second electrode disposed opposite to the first electrode; and an organic layer located between the first electrode and the second electrode or outside one or more of the first electrode and the second electrode, wherein the organic layer contains any one or a combination of at least two of the aromatic amine derivatives.

The beneficial effects are that:

The aromatic amine derivative disclosed by the invention has excellent hole transport capability, so that the aromatic amine derivative can be used as a hole transport layer material of an organic electroluminescent device, and compared with the prior material, the aromatic amine derivative can be used for manufacturing the organic electroluminescent device with high luminous efficiency and long service life. Furthermore, the aromatic amine derivative has good charge generation capability and stability, is used as a P-type material of a charge generation layer, and is beneficial to improving charge generation efficiency and device stability, so that a high-performance laminated organic electroluminescent device is obtained.

Detailed Description

The present application is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are meant to be illustrative of the application and not limiting the scope of the application, and that modifications of the application, which are all equivalent to those skilled in the art to which the application pertains, are within the scope of the application as claimed.

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

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

Examples of the halogen according to the present invention may include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The term "C1-C15" in the "substituted or unsubstituted C1-C15 alkyl" as used herein refers to the number of carbon atoms in the unsubstituted "alkyl" and does not include the number of carbon atoms in the substituent. The term "C6-C30" in the "substituted or unsubstituted C6-C30 aryl" refers to the number of carbon atoms in the unsubstituted "aryl" and does not include the number of carbon atoms in the substituent. And so on.

The alkyl refers to a monovalent group formed by removing one hydrogen atom in an alkane molecule. The number of carbon atoms of the alkyl group is from C1 to C15, preferably from C1 to C10. Examples of such alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl and the like.

The chain alkyl group having more than three carbon atoms according to the present invention includes isomers thereof, for example, propyl group includes n-propyl group, isopropyl group, butyl group includes n-butyl group, sec-butyl group, isobutyl group, tert-butyl group. And so on.

"Substituted or unsubstituted silyl" as used herein refers to-Si (R _W)₃ groups wherein each R _W is the same or different and is selected from the group consisting of: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted alkyl of C1 to C30, substituted or unsubstituted alkenyl of C1 to C30, substituted or unsubstituted cycloalkyl of C3 to C30, substituted or unsubstituted aryl of C6 to C60, substituted or unsubstituted heteroaryl of C2 to C60, fused cyclic group of substituted or unsubstituted alicyclic of C3 to C30 with aromatic ring of C6 to C60, fused cyclic group of substituted or unsubstituted alicyclic of C3 to C30 with heteroaromatic ring of C2 to C60, preferably, each R _W is the same or different and is selected from the group consisting of: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, the number of carbon atoms of the alkyl group is preferably 1 to 20, preferably 1 to 15, more preferably 1 to 10, most preferably 1 to 8, the number of carbon atoms of the cycloalkyl group is preferably 3 to 20, preferably 3 to 15, more preferably 3 to 10, most preferably 3 to 7, the number of carbon atoms of the aryl group is preferably 6 to 20, preferably 6 to 13, more preferably 6 to 12, most preferably 6 to 10, preferably, each R _W is the same or different and is selected from the group consisting of: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted butyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted heptyl, substituted or unsubstituted or substituted or the substituted or unsubstituted or substituted or unsubstituted or substituted or, A substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group. By "alkylsilyl" is meant that at least one substituent R _W of the silyl group (-SiH ₃) is an alkyl group, preferred alkylsilyl groups include, but are not limited to, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl; the "arylsilyl group" means that at least one substituent R _W of the silyl group (-SiH ₃) is an aryl group, and preferable arylsilyl groups specifically include triphenylsilyl group, diphenylmethylsilyl group, phenyldimethylsilyl group, and the like, but are not limited thereto.

The aryl refers to a monovalent group formed by removing one hydrogen atom from the aromatic nucleus carbon of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl groups, polycyclic aryl groups, and condensed ring aryl groups. The number of carbon atoms of the aryl group is from C6 to C30, preferably from C6 to C20, more preferably from C6 to C15, and still more preferably from C6 to C12. Examples of the aryl group include, but are not limited to, phenyl, biphenyl, terphenyl, tetrabiphenyl, pentacenyl, naphthyl, indenyl, indanyl, dihydronaphthyl, tetrahydronaphthyl, phenanthryl, triphenylenyl, anthracenyl, pyrenyl, fluorenyl, spirobifluorenyl, spiroanthracenyl, benzofluorenyl, benzospirobifluorenyl, and the like.

The cycloaliphatic radical as used herein refers to aliphatic hydrocarbons having 3 to 15 carbon atoms, which may be fully unsaturated or partially unsaturated. Such as, but not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, cycloheptene, and the like. The plurality of monocyclic hydrocarbons may also be linked in a variety of ways: two rings in the molecule can share one carbon atom to form a spiro ring; the two carbon atoms on the ring can be connected by a carbon bridge to form a bridge ring; several rings may also be interconnected to form a cage structure such as, but not limited to, adamantane, norbornane, camphene, and the like.

The fused ring group of the alicyclic ring and the aromatic ring refers to the general term that after the alicyclic ring and the aromatic ring are fused together, one hydrogen atom is removed, and a monovalent group is left. Examples of the condensed cyclic group of the alicyclic ring and aromatic ring may include indanyl, indenyl, tetrahydronaphthyl, dihydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclobutenyl, benzocycloheptyl, benzocycloheptenyl, and the like, but are not limited thereto. The alicyclic ring has a carbon number of 3 to 15, preferably 3 to 10. The number of carbon atoms of the aromatic ring is from C6 to C30, preferably from C6 to C18, and more preferably from C6 to C12.

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

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

In this specification, when a substituent is not fixed in position on a ring, it is meant that it can be attached to any of the corresponding selectable positions of the ring.

For example, the number of the cells to be processed,Can represent/>Can represent/>Can represent/>And so on.

In the present invention, "two adjacent groups may be linked to each other to form a substituted or unsubstituted ring" means that the two adjacent groups are bonded to each other and optionally aromatized to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle. The hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. The heterocycle may include aliphatic or aromatic heterocycles. The aliphatic hydrocarbon ring may be a saturated aliphatic hydrocarbon ring or an unsaturated aliphatic hydrocarbon ring, and the aliphatic heterocyclic ring may be a saturated aliphatic heterocyclic ring or an unsaturated aliphatic heterocyclic ring. The hydrocarbon ring and the heterocyclic ring may be a single ring or a polycyclic group. In addition, a ring formed by bonding adjacent groups may be linked to another ring to form a spiro structure. As exemplified below:

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

The invention provides an aromatic amine derivative, which has a general formula shown in a structural formula 1,

the X is selected from O atoms and N (R _d);

the X ₁ is selected, identically or differently, from the group consisting of O atom, S atom, C (R _j R_k)、N(R_p) for each occurrence;

The L ₃ is selected from a single bond or a group as shown below:

The Y ₁, at each occurrence, is identically or differently selected from O atoms, S atoms, C (R _m R_n)、N(R_t);

Preferably, in the formula 1Any one selected from the following groups:

The R ₃、R₄ groups, for each occurrence, are identically or differently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted: any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, fluorenyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, or combinations thereof; or between the adjacent two R ₃ and between the two R ₄ can be connected with each other to form a substituted or unsubstituted ring;

The R ₉、R₁₀ groups, for each occurrence, are identically or differently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted: any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, fluorenyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, or combinations thereof; or the adjacent two R ₉ can be connected with each other to form a substituted or unsubstituted ring;

Said f ₁ is selected, identically or differently, from 1,2,3, 4, or 5 for each occurrence; said f ₂ is selected, identically or differently, from 1,2,3, or 4 for each occurrence; said f ₃ is selected, identically or differently, from 1,2,3, 4, 5,6, or 7 for each occurrence; said f ₄ is selected, identically or differently, from 1,2,3, 4, 5,6,7, 8, or 9 for each occurrence; said f ₅ is selected, identically or differently, from 1,2,3, 4, 5 or 6 for each occurrence; said f ₆ is selected, identically or differently, from 1,2,3, 4, 5,6,7, or 8 for each occurrence; said f ₇ is selected, identically or differently, from 1,2,3, 4, 5,6,7, 8, 9, or 10 for each occurrence; said f ₈ is selected, identically or differently, from 1,2, or 3 for each occurrence; said f ₉ is selected identically or differently from 1 or 2 for each occurrence; the a ₁ is selected, identically or differently, from 1,2,3, 4, 5, or 6 for each occurrence; the b ₁ is selected identically or differently from 1,2,3, 4, 5 or 6 for each occurrence.

Preferably, in the formula 1Any one selected from the following groups:

The R ₇、R₈ groups, for each occurrence, are identically or differently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted: any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, fluorenyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, or combinations thereof; or between the adjacent two R ₇ and between the two R ₈ can be connected with each other to form a substituted or unsubstituted ring;

The R _g is selected from hydrogen, deuterium, substituted or unsubstituted following groups: any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, or combinations thereof;

Said c ₁ is selected, identically or differently, from 1,2, 3, 4, 5 or 6 for each occurrence; said c ₂ is selected, identically or differently, from 1,2, 3, 4, 5, 6, 7, or 8 for each occurrence; said c ₃ is selected, identically or differently, from 1,2, 3, 4, 5, 6, or 7 for each occurrence; said c ₄ is selected, identically or differently, for each occurrence, from 1,2, 3, 4, 5, 6, 7, 8, 9, or 10; d ₁ is, for each occurrence, identically or differently selected from 1,2, 3, 4, 5 or 6; the d ₂ is selected, identically or differently, from 1,2, 3, 4, 5, 6, 7 or 8 for each occurrence.

Preferably, in the formula 1Any one selected from the following groups:

The R _d is selected from hydrogen, deuterium, substituted or unsubstituted following groups: any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, silyl, or combinations thereof.

Preferably, L ₁、L₂ is independently selected from a single bond or any one of the following groups:

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The R ₁₁ groups, for each occurrence, are identically or differently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted: any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, or combinations thereof;

The R ₁₃ groups, for each occurrence, are identically or differently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted: any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, or combinations thereof;

the R _p、R_q groups, for each occurrence, are identically or differently selected from the following substituted or unsubstituted groups: any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, or combinations thereof;

said g ₁ is selected, identically or differently, from 1, 2, 3, or 4 for each occurrence; said g ₂ is selected identically or differently from 1, 2, or 3 for each occurrence; said g ₃ is selected identically or differently from 1 or 2 for each occurrence; said g ₄ is selected, identically or differently, from 1, 2, 3, 4, 5, or 6 for each occurrence; the g ₅ is selected, identically or differently, from 1, 2, 3, 4, 5, 6, 7, or 8 for each occurrence.

Further preferably, the L ₁、L₂ is independently selected from a single bond or any one of the following groups:

preferably, the L ₃ is selected from a single bond or any one of the following groups:

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The R ₁₂ groups, for each occurrence, are identically or differently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted: any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, or combinations thereof;

the R ₁₄ groups, for each occurrence, are identically or differently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted: any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, or combinations thereof;

The R _s、R_t groups, for each occurrence, are identically or differently selected from the following substituted or unsubstituted groups: any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, indenyl, tetrahydronaphthyl, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, silyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, or combinations thereof;

Each occurrence of said h ₁ is identically or differently selected from 1, 2, 3, or 4; each occurrence of said h ₂ is identically or differently selected from 1, 2, or 3; each occurrence of said h ₃ is identically or differently selected from 1 or 2; each occurrence of said h ₄ is identically or differently selected from 1, 2, 3,4, 5, or 6; the h ₅ is selected, identically or differently, from 1, 2, 3,4, 5, 6, 7, or 8 for each occurrence; each occurrence of said h ₆ is identically or differently selected from 1, 2, 3,4, or 5; the h ₇ is selected, identically or differently, from 1, 2, 3,4, 5, 6, 7, 8, 9 or 10 for each occurrence.

Further preferably, the L ₃ is selected from a single bond or any one of the following groups:

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most preferably, the aromatic amine derivative represented by formula 1 is selected from any one of the chemical structures shown below:

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The specific chemical structures of the aromatic amine derivative of the formula 1 according to the present invention are listed above, but the present invention is not limited to the chemical structures listed, and substituents are included in the aromatic amine derivative of the formula 1.

Further, the present invention also provides an organic electroluminescent device, including: a first electrode; a second electrode disposed opposite to the first electrode; and an organic layer located between the first electrode and the second electrode or outside one or more of the first electrode and the second electrode, wherein the organic layer contains any one or a combination of at least two of the aromatic amine derivatives.

Preferably, the organic layer includes a hole transport region, a light emitting layer, an electron transport region, and a capping layer, and at least one layer of the hole transport region contains any one or a combination of at least two of the aromatic amine derivatives according to the present invention.

Preferably, the organic layer includes a hole transport region, two or more light emitting layers, an electron transport region, and a capping layer, and an N-type charge generation layer and a P-type charge generation layer are disposed between each light emitting layer, where the P-type charge generation layer contains any one or a combination of at least two of the aromatic amine derivatives according to the present invention.

Preferably, the first electrode is an anode, the second electrode is a cathode, or alternatively, the first electrode is a cathode and the second electrode is an anode.

Preferably, the hole transport region comprises at least one of a hole injection layer, a hole transport layer, and an electron blocking layer, the hole injection layer is located between the anode and the cathode, the hole transport layer is located between the hole injection layer and the cathode, the electron blocking layer is located between the hole transport layer and the cathode, and at least one of the hole injection layer, the hole transport layer, and the electron blocking layer contains the aromatic amine derivative of the present invention.

Preferably, the hole transport region comprises a hole transport layer comprising the aromatic amine derivative according to the present invention.

Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer is positioned between the first hole transport layer and the cathode, and the first hole transport layer contains the aromatic amine derivative.

Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer is positioned between the first hole transport layer and the cathode, and the second hole transport layer contains the aromatic amine derivative.

Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer is positioned between the first hole transport layer and the cathode, and the first hole transport layer and the second hole transport layer contain the aromatic amine derivative.

Preferably, the hole transport layer comprises a first hole transport layer, a second hole transport layer and a third hole transport layer, the second hole transport layer is located between the first hole transport layer and the cathode, the third hole transport layer is located between the second hole transport layer and the cathode, and at least one of the first hole transport layer, the second hole transport layer and the third hole transport layer contains the aromatic amine derivative.

Preferably, the hole transport layer comprises a first hole transport layer, a second hole transport layer and a third hole transport layer, the second hole transport layer is located between the first hole transport layer and the cathode, the third hole transport layer is located between the second hole transport layer and the cathode, and the first hole transport layer comprises the aromatic amine derivative according to the present invention.

Preferably, the hole transport layer comprises a first hole transport layer, a second hole transport layer and a third hole transport layer, the second hole transport layer is located between the first hole transport layer and the cathode, the third hole transport layer is located between the second hole transport layer and the cathode, and the second hole transport layer comprises the aromatic amine derivative according to the present invention.

Preferably, the hole transport layer comprises a first hole transport layer, a second hole transport layer and a third hole transport layer, the second hole transport layer is located between the first hole transport layer and the cathode, the third hole transport layer is located between the second hole transport layer and the cathode, and the third hole transport layer comprises the aromatic amine derivative according to the present invention.

Preferably, the organic electroluminescent device of the present invention is a single-layer organic electroluminescent device or a stacked organic electroluminescent device, wherein the single-layer organic electroluminescent device is an organic electroluminescent device containing one light emitting unit, and the stacked organic electroluminescent device is an organic electroluminescent device formed by connecting N (N is greater than or equal to 2) independent light emitting units in series through a charge generation layer.

Preferably, the organic electroluminescent device according to the present invention is a single-layered organic electroluminescent device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate.

Preferably, the organic electroluminescent device according to the present invention is a stacked organic electroluminescent device, wherein a first light emitting unit emitting light of a first color, an nth light emitting unit emitting light of an nth color, and a charge generation layer uniformly controlling charges between the first light emitting unit and the nth light emitting unit are formed between an anode and a cathode, and an N-type charge generation layer and a P-type charge generation layer are included between light emitting units adjacent to each other.

Preferably, the P-type charge generation layer contains the aromatic amine derivative of the present invention, or the P-type charge generation layer may be formed by doping with other materials using the aromatic amine derivative of the present invention.

The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.

The material of each layer of thin film in the organic electroluminescent device is not particularly limited, and materials known in the art can be used. The organic layer of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device are described below:

The anode of the present invention preferably uses a metal, an alloy, a conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0eV or more). The material for the anode of the present invention may comprise: metals or alloys thereof, metal oxides, laminates, conductive polymers, combinations of metals and oxides, and the like, for example, nickel (Ni), platinum (Pt), vanadium (V), silver (Ag), gold (Au), zinc oxide (ZnO), indium Tin Oxide (ITO), indium Zinc Oxide (IZO), indium oxide (In ₂O₃), indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO), polypyrrole, polyaniline, zinc oxide: aluminum (ZnO: al), and the like. But is not limited thereto.

The hole injection material according to the present invention is preferably a material capable of reducing the interface barrier between the anode and the hole transport layer. Materials described below, polycyano conjugated organic compounds, alkylene compounds, phthalocyanine metal complexes, aromatic amine derivatives, polymers, and the like. Specific examples may include metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile hexaazabenzophenanthrene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, and polyaniline-based and polythiophene-based conductive polymers, etc., but are not limited thereto, and may further include additional compounds capable of p-doping.

The hole transporting material according to the present invention is preferably a material capable of receiving holes from an anode or a hole injecting layer and transporting the holes to a light emitting layer, and has a high hole mobility and a good stability. The hole transport material of the present invention is located between the anode and the light emitting layer, or between the hole injection layer and the light emitting layer in the presence of the hole injection layer, and may have a single-layer structure or a multilayer structure. As the hole transport layer material, for example, an aromatic amine compound, a carbazole derivative, an anthracene derivative, a polymer, or the like can be used. Specific examples may include 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB), N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1,1' -biphenyl ] -4,4' -diamine (TPD), 4-phenyl-4 ' - (9-phenylfluoren-9-yl) triphenylamine (BAFLP), 4' -bis [ N- (9, 9-dimethylfluoren-2-yl) -N-phenylamino ] biphenyl (DFLDPBi), 4' -tris (N, N-diphenylamino) triphenylamine (TDATA), 4', 4' -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (MTDATA), 4' -bis [ N- (spiro-9, 9' -bifluorene-2-yl) -N-phenylamino ] biphenyl (BSPB), 4' -bis (9-Carbazolyl) Biphenyl (CBP), 9- [4- (9-carbazolyl) phenyl ] -10-phenylanthracene (CzPA), 9-phenyl-3- [4- (10-phenyl-9-anthracenyl) phenyl ] -9H-carbazole (PCzPA), 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene (t-BuDNA), 9, 10-bis (2-naphthyl) anthracene (DNA), 9, 10-diphenylanthracene (DPAnth), poly (N-vinylcarbazole) (PVK), poly (4-vinyltriphenylamine) (PVTPA), an aromatic amine derivative represented by the formula 1 of the present invention, and the like, but are not limited thereto. The aromatic amine derivative represented by formula 1 of the present invention is preferable.

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

The light-emitting layer according to the present invention may contain only a guest material, or may take the form of a guest material dispersed in a host material, wherein the host material may be composed of one or more materials.

As the host material of the light emitting layer of the present invention, there may be included a condensed aromatic ring derivative, a heterocyclic compound, etc., such as 9, 10-bis (2-naphthyl) Anthracene (ADN), 10' -bis (biphenyl-4-yl) -9,9' -Bianthracene (BANE), 1,3, 5-tris (pyren-1-yl) benzene (TPB ₃), 1,3, 5-tris (carbazole-9-yl) benzene (TCP), 14,4',4 "-tris (carbazole-9-yl) triphenylamine (TCTA), 4' -bis (carbazole-9-yl) -2,2' -dimethylbiphenyl (CDBP), 4' -bis (carbazole-9-yl) biphenyl (CBP), 9- [4- (10-phenyl-9-anthracenyl) phenyl ] -9H-carbazole (CzPA), 3, 6-diphenyl-9- [4- (10-phenyl-9-anthracenyl) phenyl ] -9H-carbazole (DPCzPA), 9, 10-bis (3, 5-diphenyl) anthracene (N, N ' -bis (carbazole-9-yl) -2,2' -dimethylbiphenyl (CDBP), 4' -bis (4-phenyl-9-anthracenyl) phenyl ] -9H-carbazole (CzPA), 9-dimethylfluoren-2-yl) -N-phenylamino ] biphenyl (DFLDPBi), 4 '-bis [ N- (spiro-9, 9' -bifluorene-2-yl) -N-phenylamino ] biphenyl (BSPB), and the like, but are not limited thereto.

As the light emitting layer guest material of the present invention, aromatic amine derivatives, condensed aromatic ring derivatives, heterocyclic derivatives, metal complexes, etc., may be included, for example, 4' -bis (4- (9H-carbazol-9-yl) styryl) biphenyl (BSB ₄), 4' -bis [4- (diphenylamino) styryl ] biphenyl (BDAVBi), 10' -bis (3, 5-bis (trifluoromethyl) phenyl) -9,9' -bianthracene (Ban- (3, 5) -CF ₃), 5,6,11, 12-tetraphenyltetracene (Rubrene), coumarin 545T (C-525T) tris (2-phenyl-3-methyl-pyridine) iridium (Ir (3 mppy) ₃), bis (2- (naphthalen-2-yl) pyridine) (acetylacetone) iridium (III) (Ir (npy) ₂ acac), tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃), bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2' -picolinine (C) tris (2-phenyl-3-methyl-picolinine) iridium (Ir) 2', bis (2 ' -bipyridyl) iridium (3-phenylpyridine) iridium (Ir (npy) iridium (3 mppy) and bis (2 ' -bipyridyl) iridium (3 ', 2' -bipyridyl) iridium (3, 2' -bipyridyl), c2' ] iridium (III) acetylacetonate (FIracac) and the like, but is not limited thereto.

The hole blocking layer material of the present invention needs to have a good hole blocking capability in order to block holes in the light emitting layer. As described below, imidazole derivatives, phenanthroline derivatives, metal complexes, triazine derivatives, and the like. Specific examples may include 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 2- (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (HNBphen), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1, 1' -biphenyl-4-hydroxy) aluminum (BAlq), 2- (9, 9-dimethyl-9H-fluoren-2-yl) 4- (9, 9-diphenyl-9H-fluoren-4-yl) -6-phenyl-1, 3, 5-triazine, and the like, but are not limited thereto.

The electron transport layer material is preferably a material with better electron transport capability and better stability. The structure may be a single-layer structure or a multi-layer structure. As described below, imidazole derivatives, phenanthroline derivatives, pyridine derivatives, triazine derivatives, quinoline derivatives, oxadiazole derivatives, triazole derivatives, metal complexes and the like. Specific examples may include 2- (4- (9, 10-bis (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 2- (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (HNBphen), 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 3'- [5' - [3- (3-pyridinyl) phenyl ] (TmPyPB), 1, 4-bis (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) naphthalene 2- (3- (phenanthren-9-yl) -5- (pyridin-3-yl) phenyl) -4, 6-diphenyl-1, 3, 5-triazine, 1,3, 5-tris (4- (pyridin-4-yl) quinolin-2-yl) benzene (TPyQB), 2, 5-bis- (4-naphthyl) -1,3, 4-oxadiazole (BND), 3- (biphenyl-4-yl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), lithium 8-hydroxyquinolinate (LiQ), aluminum tris (8-hydroxyquinoline) (III) (Alq), aluminum tris (4-methyl-8-hydroxyquinoline) (Almq 3), beryllium bis (10-hydroxybenzo [ h ] quinoline) (BeBq 2), bathophenanthroline (BPhen), bathocuproine (BCP), poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (pyridine-3, 5-diyl) ] (PF-Py), and the like, but are not limited thereto.

The electron injection layer material according to the present invention is preferably a material capable of reducing the interface barrier between the cathode and the electron transport layer. Alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca) and strontium (Sr), rare earth metals such as europium (Eu) and ytterbium (Yb), and compounds containing these metals can be used. Examples of such a compound include: alkali metal oxides, alkali metal halides, alkali metal-containing organic complexes, alkaline earth metal oxides, alkaline earth metal halides, alkaline earth metal-containing organic complexes, rare earth metal oxides, rare earth metal halides, and rare earth metal-containing organic complexes. In addition, a plurality of these compounds may be used in combination.

The cathode of the present invention preferably uses small work function (specifically, a work function of 3.8eV or less) metals, alloys, conductive compounds, mixtures thereof, and the like. The material for the cathode of the present invention may comprise: metals or alloys thereof, multilayer structural materials, and the like, for example, silver (Ag), aluminum (Al), magnesium (Mg), tin (Sb), magnesium silver (Mg: ag), calcium/magnesium (Ca/Mg), and the like. But is not limited thereto.

The cover layer according to the present invention may have a single layer structure of a single substance, or may have a single layer structure or a multilayer structure of different substances. The material for the cover layer may be an organic or inorganic material having an appropriate refractive index, and may be, for example, metal halides, oxides, nitrides, oxynitrides, sulfides, selenides, aromatic compounds, heteroaromatic compounds, aromatic amine compounds, etc., and specific examples may include LiF、CsF、MgF₂、CaF₂、CsCl、CuI、V₂O₅、WO₃、MoO₃、TiO₂、ZrO、ZnO、SiO₂、 tris (8-hydroxyquinoline) aluminum (III) (Alq ₃), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4' -bis (9-carbazole) biphenyl (abbreviated CBP), etc., but are not limited thereto.

The N-type charge generating material of the present invention may be selected from one of the following materials or a combination thereof: tris- (8-hydroxyquinolinolate) aluminum (Alq 3), 2-biphenyl-4-yl-5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), spiro-PBD, lithium quinolinolate (Liq), 1,3, 5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBi), bis (2-methyl-8-quinolinato-N1, O8) - (1, 1' -biphenyl-4-phenolato) aluminum (BAlq), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-bis (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (NBphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 3- (4-biphenyl) -4-phenyl-5-tert-butylphenyl-1, 2, 4-Triazole (TAZ), 4- (naphthalen-1-yl) -3, 5-diphenyl-4H-1, 2, 4-triazole (NTAZ), 1,3, 5-tris (p-pyridin-3-yl-phenyl) benzene (TpPyPB), 2,4, 6-tris (3 ' - (pyridin-3-yl) biphenyl-3-yl) 1,3, 5-triazine (TmPPPyTz), poly [9, 9-bis (3 ' - ((N), n-dimethyl) -N-ethylamino) -propyl) -2, 7-fluoren ] -alterna-2, 7- (9, 9-dioctylfluorene) ] (PFNBr), triphenylquinoxaline (TPQ), diphenyl-4-triphenylsilyl-phenylphosphine oxide (TSPO 1), and the like, but is not limited thereto. In addition, an auxiliary N-type charge generating material may be included. For example, the auxiliary N-type charge generating material may be an alkali metal, such as Li, cs, K, rb, na or Fr, etc., but is not limited thereto, or an alkaline earth metal, such as Be, mg, ca, sr, ba or Ra, etc., but is not limited thereto.

The P-type charge generating material of the present invention may comprise one of the following materials or a combination thereof: 4,4',4 "-tris (3-methylphenylamino) triphenylamine (MTDATA), 4',4" -tris (N, N-diphenyl-amino) triphenylamine (NATA), 4',4 "-tris (N- (naphthalen-1-yl) -N-phenyl-amino) triphenylamine (1T-NATA), 4',4" -tris (N- (naphthalen-2-yl) -N-phenyl-amino) triphenylamine (2T-NATA), copper phthalocyanine (CuPc), tris (4-carbazolyl-9-yl-phenyl) amine (TCTA), N ' -diphenyl-N, N ' -bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine (NPD), 1,4,5,8,9,11-hexaazatriphenylhexa-carbonitrile (bipyrazino [2, 3-f); 2'3' -h ] quinoxaline-2, 3,6,7,10, 11-hexacarbonitrile (HAT-CN), 1,3, 5-tris [4- (diphenylamino) phenyl ] benzene (TDAPB), poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT/PSS) and N- (biphenyl-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine, the aromatic amine derivative of the present invention, and the like, but are not limited thereto, and the aromatic amine derivative represented by the formula 1 of the present invention is preferable.

The method for producing the thin films of each layer in the organic electroluminescent device of the present invention is not particularly limited, and vacuum deposition, sputtering, spin coating, spray coating, screen printing, laser transfer, etc. may be used, but are not limited thereto. The film thickness of each layer is not particularly limited, and in general, if the film thickness is too small, defects such as pinholes tend to occur, whereas if it is too large, a high driving voltage is required and efficiency is deteriorated, so that it is usually 5nm to 10 μm, more preferably 10nm to 0.2 μm.

The organic electroluminescent device is mainly applied to the technical field of information display, and is widely applied to various information displays in the aspect of information display, such as tablet computers, televisions, mobile phones, intelligent watches, digital cameras, VR (virtual reality), vehicle-mounted systems, wearable equipment, lighting equipment and the like.

Synthetic examples

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

Instrument: g2—si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); vario EL cube organic element analyzer (Elementar, germany).

The method for producing the aromatic amine derivative of the structural formula 1 of the present invention is not particularly limited, and conventional methods known to those skilled in the art can be employed. For example, carbon-nitrogen coupling reaction, carbon-carbon coupling reaction, etc., for example, the aromatic amine derivative of the structural formula 1 of the present invention can be prepared by using the synthetic route shown below.

Synthetic route 1:

Synthetic route 2:

the X ₁、X₂ is a halogen atom, for example, a halogen atom, I, br, cl, which may be the same or different, selected from the group consisting of those described below.

R ₁～R₈、L₁～L₃、R_a -Rc and a-e are all as described in the invention.

Synthesis example 1: preparation of intermediate C-91

To a reaction flask, C-32 (11.03 g,56.00 mmol), d-91 (8.76 g,56.00 mmol), potassium carbonate (11.61 g,84.00 mmol), pd (PPh ₃)₄ (0.77 g,0.67 mmol), and 280mL toluene/ethanol/water (2:1:1) mixed solvent were added under argon atmosphere, the mixture was stirred, the above-mentioned reaction system was heated under reflux for 5.5h, after the reaction was completed, cooled to room temperature, toluene was added and the phases were separated, the toluene phase was washed three times with distilled water, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, cooled and crystallized, suction filtration, and the obtained solid was recrystallized from toluene to give intermediate C-91 (10.12 g, yield 79%); HPLC purity +.99.80%. M/z:228.0358 (theoretical value: 228.0342).

Other intermediates required in the present invention were synthesized according to the above synthesis method, and the relevant raw materials are shown in table 101:

Table 101:

Synthesis example 2: preparation of Compound 3

Preparation of intermediate I-3:

A-3 (12.56 g,60.00 mmol), b-3 (23.84 g,60.00 mmol), pd (OAc) ₂ (0.13 g,0.60 mmol), sodium tert-butoxide (11.53 g,120.00 mmol), tri-tert-butylphosphine (1.2 mL,0.5M in toluene) and 300mL of toluene were added to the reaction flask under argon, and the mixture was stirred and heated to reflux for 4h. After the reaction, cooling to room temperature, adding dichloromethane and distilled water into the reaction liquid, stirring, and extracting in a liquid-separated mode. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, and toluene was used: ethanol=10:1 recrystallisation gives intermediate I-3 (24.60 g, 78% yield) with purity of > 99.87% by HPLC. Mass spectrum m/z:525.2440 (theoretical value: 525.2457). Preparation of compound 3:

To the reaction flask were added I-3 (21.03 g,40.00 mmol), c-3 (7.88 g,40.00 mmol), pd ₂(dba)₃ (0.46 g,0.40 mmol), sodium t-butoxide (7.69 g,80.00 mmol), BINAP (0.50 g,0.80 mmol) and 200mL toluene under argon, and the mixture was stirred and heated to reflux for 6h. After the reaction was completed, cooled to room temperature, filtered through celite, the filtrate was concentrated, recrystallized from toluene, suction-filtered and rinsed with toluene to obtain recrystallized solid, to give compound 3 (19.51 g, yield 76%), purity of solid was not less than 99.97% by HPLC. Mass spectrum m/z:641.2729 (theoretical value: 641.2719). Theoretical element content (%) C ₄₈H₃₅ NO: c,89.83; h,5.50; n,2.18. Measured element content (%): c,89.86; h,5.48; n,2.15.

Synthesis example 3: preparation of Compound 32

According to the method of example 2, b-3 was replaced with equimolar b-32 and c-3 was replaced with equimolar c-32 to give compound 32 (20.10 g), and the purity of the solid was not less than 99.95% by HPLC. Mass spectrum m/z:669.3020 (theoretical value: 669.3032). Theoretical element content (%) C ₅₀H₃₉ NO: c,89.65; h,5.87; n,2.09. Measured element content (%): c,89.63; h,5.85; n,2.12.

Synthesis example 4: preparation of Compound 41

According to the method of example 2, b-3 was replaced with equimolar b-41 and c-3 was replaced with equimolar c-41 to give compound 41 (21.72 g), and the purity of the solid was not less than 99.92% by HPLC. Mass spectrum m/z:753.3985 (theoretical value: 753.3971). Theoretical element content (%) C ₅₆H₅₁ NO: c,89.20; h,6.82; n,1.86. Measured element content (%): c,89.17; h,6.84; n,1.88.

Synthesis example 5: preparation of Compound 44

According to the method of example 2, b-3 was replaced with equimolar b-44 and c-3 was replaced with equimolar c-32 to give compound 44 (20.85 g), and the purity of the solid was not less than 99.91% by HPLC. Mass spectrum m/z:713.3125 (theoretical value: 713.3114). Theoretical element content (%) C ₅₁H₄₃ NOSi: c,85.79; h,6.07; n,1.96. Measured element content (%): c,85.81; h,6.04; n,1.95.

Synthesis example 6: preparation of Compound 48

According to the method of example 2, b-3 was replaced with equimolar b-48 and c-3 was replaced with equimolar c-32 to give compound 48 (20.91 g), and the purity of the solid was not less than 99.94% by HPLC. Mass spectrum m/z:717.3018 (theoretical value: 717.3032). Theoretical element content (%) C ₅₄H₃₉ NO: c,90.34; h,5.48; n,1.95. Measured element content (%): c,90.37; h,5.46; n,1.97.

Synthesis example 7: preparation of Compound 58

According to the method of example 2, substituting a-3 with equimolar a-58, substituting b-3 with equimolar b-58, and substituting c-3 with equimolar c-32, compound 58 (20.68 g) was obtained, and the purity of the solid as measured by HPLC was 99.96%. Mass spectrum m/z:717.3016 (theoretical value: 717.3032). Theoretical element content (%) C ₅₄H₃₉ NO: c,90.34; h,5.48; n,1.95. Measured element content (%): c,90.37; h,5.46; n,1.97. Synthesis example 8: preparation of Compound 78

According to the method of example 2, c-3 was replaced with equimolar c-78 to give compound 78 (18.89 g), and the purity of the solid was 99.93% or more as measured by HPLC. Mass spectrum m/z:646.3047 (theoretical value: 646.3032). Theoretical element content (%) C ₄₈H₃₀D₅ NO: c,89.13; h,6.23; n,2.17. Measured element content (%): c,89.16; h,6.19; n,2.15.

Synthesis example 9: preparation of Compound 84

According to the method of example 2, b-3 was replaced with equimolar b-84 and c-3 with equimolar c-32 to give compound 84 (19.93 g), which was found to have a solid purity of 99.93% or more by HPLC. Mass spectrum m/z:691.2860 (theoretical value: 691.2875). Theoretical element content (%) C ₅₂H₃₇ NO: c,90.27; h,5.39; n,2.02. Measured element content (%): c,90.25; h,5.41; n,2.06.

Synthesis example 10: preparation of Compound 91

According to the method of example 2, c-3 was replaced with equimolar c-91 to give compound 91 (21.82 g), and the purity of the solid was 99.96% or more as measured by HPLC. Mass spectrum m/z:717.3049 (theoretical value: 717.3032). Theoretical element content (%) C ₅₄H₃₉ NO: c,90.34; h,5.48; n,1.95. Measured element content (%): c,90.32; h,5.46; n,1.98.

Synthesis example 11: preparation of Compound 94

According to the method of example 2, a-3 was replaced with equimolar a-94 and C-3 was replaced with equimolar C-94 to give compound 94 (21.00 g), and the purity of the solid was not less than 99.94% by HPLC. Mass spectrum m/z:717.3048 (theoretical value: 717.3032). Theoretical element content (%) C ₅₄H₃₉ NO: c,90.34; h,5.48; n,1.95. Measured element content (%): c,90.31; h,5.47; n,1.97.

Synthesis example 12: preparation of Compound 95

According to the method of example 2, C-3 was replaced with equimolar C-95 to give compound 95 (20.10 g), and the purity of the solid was not less than 99.91% by HPLC. Mass spectrum m/z:717.3046 (theoretical value: 717.3032). Theoretical element content (%) C ₅₄H₃₉ NO: c,90.34; h,5.48; n,1.95. Measured element content (%): c,90.32; h,5.45; n,1.94.

Synthesis example 13: preparation of Compound 99

According to the method of example 2, the substitution of a-3 for equimolar a-99, b-3 for equimolar b-99 and C-3 for equimolar C-99 gave compound 99 (21.91 g), with a solid purity of 99.92% or higher as measured by HPLC. Mass spectrum m/z:793.3335 (theoretical value: 793.3345). Theoretical element content (%) C ₆₀H₄₃ NO: c,90.76; h,5.46; n,1.76. Measured element content (%): c,90.74; h,5.44; n,1.79.

Synthesis example 14: preparation of Compound 109

According to the method of example 2, the substitution of a-3 for equimolar a-109, b-3 for equimolar b-109 and C-3 for equimolar C-109 gave compound 109 (23.08 g) having a solid purity of 99.93% or more as measured by HPLC. Mass spectrum m/z:911.4141 (theoretical value: 911.4127). Theoretical element content (%) C ₆₉H₅₃ NO: c,90.85; h,5.86; n,1.54. Measured element content (%): c,90.88; h,5.83; n,1.56. Synthesis example 15: preparation of Compound 122

According to the method of example 2, the substitution of a-3 for equimolar a-122, b-3 for equimolar b-122, and C-3 for equimolar C-122 gave compound 122 (23.75 g), with a solid purity of 99.94% or higher as measured by HPLC. Mass spectrum m/z:873.3902 (theoretical value: 873.3909). Theoretical element content (%) C ₆₆H₄₃D₄ NO: c,90.69; h,5.88; n,1.60. Measured element content (%): c,90.71; h,5.90; n,1.63.

Synthesis example 16: preparation of Compound 131

According to the method of example 2, C-3 was replaced with equimolar C-131 to give compound 131 (22.12 g), and the purity of the solid was not less than 99.91% by HPLC. Mass spectrum m/z:781.3355 (theoretical value: 781.3345). Theoretical element content (%) C ₅₉H₄₃ NO: c,90.62; h,5.54; n,1.79. Measured element content (%): c,90.65; h,5.52; n,1.81.

Synthesis example 17: preparation of Compound 142

According to the method of example 2, a-3 was replaced with equimolar a-99 and C-3 was replaced with equimolar C-142 to give compound 142 (21.22 g), and the purity of the solid was not less than 99.93% by HPLC. Mass spectrum m/z:757.3361 (theoretical value: 757.3345). Theoretical element content (%) C ₅₇H₄₃ NO: c,90.32; h,5.72; n,1.85. Measured element content (%): c,90.29; h,5.74; n,1.87.

Synthesis example 18: preparation of Compound 147

According to the method of example 2, b-3 was replaced with equimolar b-147 and C-3 was replaced with equimolar C-147 to give compound 147 (22.68 g), which was found to have a solid purity of 99.92% or more by HPLC. Mass spectrum m/z:833.3645 (theoretical value: 833.3658). Theoretical element content (%) C ₆₃H₄₇ NO: c,90.72; h,5.68; n,1.68. Measured element content (%): c,90.75; h,5.65; n,1.71.

Synthesis example 19: preparation of Compound 152

According to the method of example 2, the substitution of a-3 with equimolar a-94, b-3 with equimolar b-32 and C-3 with equimolar C-91 gave compound 152 (20.80 g) having a solid purity of 99.92% or more as measured by HPLC. Mass spectrum m/z:745.3355 (theoretical value: 745.3345). Theoretical element content (%) C ₅₆H₄₃ NO: c,90.17; h,5.81; n,1.88. Measured element content (%): c,90.14; h,5.79; n,1.91.

Synthesis example 20: preparation of Compound 155

According to the method of example 2, b-3 was replaced with equimolar b-155 and C-3 with equimolar C-91 to give compound 155 (22.29 g), solid purity not less than 99.92% by HPLC. Mass spectrum m/z:773.3649 (theoretical value: 773.3658). Theoretical element content (%) C ₅₈H₄₇ NO: c,90.00; h,6.12; n,1.81. Measured element content (%): c,90.03; h,6.15; n,1.79.

Synthesis example 21: preparation of Compound 183

According to the method of example 2, b-3 was replaced with equimolar b-183 and C-3 was replaced with equimolar C-91 to give compound 183 (19.80 g), and the purity of the solid was not less than 99.95% by HPLC. Mass spectrum m/z:727.3645 (theoretical value: 727.3659). Theoretical element content (%) C ₅₄H₂₉D₁₀ NO: c,89.10; h,6.78; n,1.92. Measured element content (%): c,89.08; h,6.75; n,1.93.

Synthesis example 22: preparation of Compound 184

According to the method of example 2, substituting a-3 with equimolar a-122, b-3 with equimolar b-184, and C-3 with equimolar C-91 gave compound 184 (20.00 g), with a solid purity of 99.94% or more as measured by HPLC. Mass spectrum m/z:724.3458 (theoretical value: 724.3471). Theoretical element content (%) C ₅₄H₃₂D₇ NO: c,89.47; h,6.39; n,1.93. Measured element content (%): c,89.45; h,6.41; n,1.90.

Synthesis example 23: preparation of Compound 198

According to the method of example 2, substituting a-3 with equimolar a-122, b-3 with equimolar b-198, and C-3 with equimolar C-198 gave compound 198 (21.82 g), which was found to have a solid purity of 99.92% or more by HPLC. Mass spectrum m/z:801.3971 (theoretical value: 801.3971). Theoretical element content (%) C ₆₀H₅₁ NO: c,89.85; h,6.41; n,1.75. Measured element content (%): c,89.82; h,6.39; n,1.78. Synthesis example 24: preparation of Compound 199

According to the method of example 2, the substitution of a-3 for equimolar a-199, b-3 for equimolar b-199 and C-3 for equimolar C-199 gave compound 199 (21.41 g) having a solid purity of 99.97% or more as measured by HPLC. Mass spectrum m/z:798.3669 (theoretical value: 798.3658). Theoretical element content (%) C ₆₀H₃₈D₅ NO: c,90.19; h,6.05; n,1.75. Measured element content (%): c,90.21; h,6.02; n,1.73.

Synthesis example 25: preparation of Compound 200

According to the method of example 2, b-3 was replaced with equimolar b-200 and C-3 was replaced with equimolar C-200 to give compound 200 (21.00 g), with a purity of not less than 99.92% as measured by HPLC. Mass spectrum m/z:771.3425 (theoretical value: 771.3439). Theoretical element content (%) C ₅₈H₃₇D₄ NO: c,90.24; h,5.87; n,1.81. Measured element content (%): c,90.27; h,5.90; n,1.78.

Synthesis example 26: preparation of Compound 223

According to the method of example 2, the substitution of a-3 for equimolar a-223, b-3 for equimolar b-223 and c-3 for equimolar c-32 gave compound 223 (23.60 g) having a solid purity of 99.93% or more as measured by HPLC. Mass spectrum m/z:893.3672 (theoretical value: 893.3658). Theoretical element content (%) C ₆₈H₄₇ NO: c,91.35; h,5.30; n,1.57. Measured element content (%): c,91.32; h,5.28; n,1.55. Synthesis example 27: preparation of Compound 239

According to the method of example 2, substitution of a-3 with equimolar a-122, b-3 with equimolar b-239 and c-3 with equimolar c-32 gave compound 239 (18.22 g) with a solid purity of 99.93% or higher as measured by HPLC. Mass spectrum m/z:669.3045 (theoretical value: 669.3032). Theoretical element content (%) C ₅₀H₃₉ NO: c,89.65; h,5.87; n,2.09. Measured element content (%): c,89.66; h,5.84; n,2.05. Synthesis example 28: preparation of Compound 245

According to the method of example 2, the substitution of a-3 for equimolar a-245, b-3 for equimolar b-245 and C-3 for equimolar C-91 gave compound 245 (21.05 g) having a solid purity of 99.94% or more as measured by HPLC. Mass spectrum m/z:773.3641 (theoretical value: 773.3658). Theoretical element content (%) C ₅₈H₄₇ NO: c,90.00; h,6.12; n,1.81. Measured element content (%): c,90.04; h,6.09; n,1.83. Synthesis example 29: preparation of Compound 254

According to the method of example 2, the substitution of a-3 for equimolar a-94, b-3 for equimolar b-254 and c-3 for equimolar c-32 gave compound 254 (20.10 g) having a solid purity of 99.96% or more as measured by HPLC. Mass spectrum m/z:717.3049 (theoretical value: 717.3032). Theoretical element content (%) C ₅₄H₃₉ NO: c,90.34; h,5.48; n,1.95. Measured element content (%): c,90.36; h,5.50; n,1.92.

Synthesis example 30: preparation of Compound 263

According to the method of example 2, b-3 was replaced with equimolar b-263 and C-3 was replaced with equimolar C-91 to give compound 263 (18.88 g), which had a solid purity of 99.96% or more as measured by HPLC. Mass spectrum m/z:655.2858 (theoretical value: 655.2875). Theoretical element content (%) C ₄₉H₃₇ NO: c,89.74; h,5.69; n,2.14. Measured element content (%): c,89.75; h,5.71; n,2.12.

Synthesis example 31: preparation of Compound 277

According to the method of example 2, substituting a-3 with equimolar a-277, substituting b-3 with equimolar b-277, and substituting C-3 with equimolar C-91 gave compound 277 (23.65 g) having a solid purity of 99.94% or more as measured by HPLC. Mass spectrum m/z:845.3643 (theoretical value: 845.3658). Theoretical element content (%) C ₆₄H₄₇ NO: c,90.85; h,5.60; n,1.66. Measured element content (%): c,90.88; h,5.57; n,1.64. Synthesis example 32: preparation of Compound 326

According to the method of example 2, b-3 was replaced with equimolar b-326 and c-3 was replaced with equimolar c-326 to obtain compound 326 (21.40 g), and the purity of the solid was not less than 99.95% by HPLC. Mass spectrum m/z:786.3984 (theoretical value: 786.3974). Theoretical element content (%) C ₅₉H₅₀N₂: c,90.04; h,6.40; n,3.56. Measured element content (%): c,90.08; h,6.38; n,3.53.

Synthesis example 33: preparation of Compound 427

According to the method of example 2, c-3 was replaced with equimolar c-427 to give compound 427 (18.85 g), and the purity of the solid was not less than 99.97% by HPLC. Mass spectrum m/z:730.3359 (theoretical value: 730.3348). Theoretical element content (%) C ₅₅H₄₂N₂: c,90.38; h,5.79; n,3.83. Measured element content (%): c,90.40; h,5.81; n,3.80.

Synthesis example 34: preparation of Compound 469

According to the method of example 2, b-3 was replaced with equimolar b-469 and C-3 was replaced with equimolar C-199 to obtain compound 469 (22.25 g), and the purity of the solid was not less than 99.95% by HPLC. Mass spectrum m/z:829.4298 (theoretical value: 829.4284). Theoretical element content (%) C ₆₂H₅₅ NO: c,89.71; h,6.68; n,1.69. Measured element content (%): c,89.69; h,6.70; n,1.71.

Synthesis example 35: preparation of Compound 484

According to the method of example 2, substituting a-3 with equimolar a-484, b-3 with equimolar b-484, and C-3 with equimolar C-484 gave compound 484 (20.65 g), with a solid purity of 99.91% or more as measured by HPLC. Mass spectrum m/z:793.3662 (theoretical value: 793.3678). Theoretical element content (%) C ₅₇H₄₃D₄ NOSi: c,86.21; h,6.47; n,1.76. Measured element content (%): c,86.23; h,6.45; n,1.74.

Synthesis example 36: preparation of Compound 560

According to the method of example 2, C-3 was replaced with equimolar C-560 to give compound 560 (20.12 g), and the purity of the solid was 99.93% or more as measured by HPLC. Mass spectrum m/z:718.2971 (theoretical value: 718.2984). Theoretical element content (%) C ₅₃H₃₈N₂ O: c,88.55; h,5.33; n,3.90. Measured element content (%): c,88.58; h,5.35; n,3.88.

Device embodiment

In the invention, an ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20min, and drying at 120deg.C. The organic materials are sublimated, and the purity is over 99.99 percent.

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

The preparation of the device is completed by adopting a vacuum evaporation system and continuously evaporating under the condition of continuous vacuum. The materials are respectively arranged in quartz crucibles of different evaporation sources, and the temperature of the evaporation sources can be controlled independently. The thermal evaporation rate of the organic material is generally set at 0.1nm/s, and the evaporation rate of the electrode metal is 0.4-0.6 nm/s. And (3) placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system is kept below 5 multiplied by 10 ^-5 Pa in the film manufacturing process, respectively evaporating an organic layer and a metal electrode by replacing a mask plate, detecting the evaporation speed by using an Infinion SQM160 quartz crystal film thickness detector, and detecting the film thickness by using a quartz crystal oscillator.

Example 1: preparation of organic electroluminescent device 1

ITO is used as an anode on the glass substrate; vacuum evaporation of 20nm NPB on anode: f4TCNQ (mass ratio 95%:5% mixed) forms a hole injection layer; forming a first hole transport layer by vacuum evaporation of 35nm of the compound 3 of the present invention on the hole injection layer; vacuum evaporating 31nm BH-1:BD-1 (mixed by mass ratio of 95% to 5%) on the first hole transport layer to form a light-emitting layer; vacuum evaporation of 35nm ET-1 on the light-emitting layer: liQ (mass ratio 1:1 mixture) forms an electron transport layer; vacuum evaporating LiF of 1.0nm on the electron transport layer to form an electron injection layer; al of 120nm was vacuum-evaporated on the electron injection layer to form a cathode.

Examples 2 to 35: preparation of organic electroluminescent devices 2 to 35

The organic electroluminescent devices 2 to 35 were obtained by replacing compound 3 in the first hole transport layer of example 1 with compound 32, compound 41, compound 44, compound 48, compound 58, compound 78, compound 84, compound 91, compound 94, compound 95, compound 99, compound 109, compound 122, compound 131, compound 142, compound 147, compound 152, compound 155, compound 183, compound 184, compound 198, compound 199, compound 200, compound 223, compound 239, compound 245, compound 254, compound 263, compound 277, compound 326, compound 427, compound 469, compound 484 and compound 560, respectively, and the other steps being the same.

Comparative examples 1 to 3: preparation of comparative organic electroluminescent devices 1 to 3

The compound 3 in the first hole transport layer of example 1 was changed to R-1, R-2, R-3, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 3.

The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 1 to 35 of the present invention and comparative examples 1 to 3 are shown in table 1.

Table 1 light emission characteristic test data of organic electroluminescent device

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Note that: t95 refers to the time taken for the brightness of the device to decay to 95% at a current density of 10mA/cm ²;

As can be seen from table 1, when the aromatic amine derivative represented by formula 1 of the present invention is used for the first hole transport layer in the organic electroluminescent device, the efficiency of the organic electroluminescent device is effectively improved and the lifetime of the device is improved, compared with comparative examples 1 to 3, further indicating that the compound of the present invention has excellent hole transport ability.

Example 36: preparation of organic electroluminescent device 36

ITO is used as an anode on the glass substrate; forming a hole injection layer by vacuum evaporation of DNTPD of 55nm on the anode; vacuum evaporating NPB of 27nm on the hole injection layer to form a first hole transport layer; vacuum evaporating the compound 3 as a second hole transport layer with the thickness of 15nm on the first hole transport layer; vacuum evaporating 30nm BH-2:BD-2 (97% by mass: 3% mixture) on the second hole transport layer to form a light-emitting layer; vacuum evaporating ET-1 of 30nm on the light-emitting layer: liQ (mass ratio 1:1 mixture) forms an electron transport layer; vacuum evaporating LiF of 1.0nm on the electron transport layer to form an electron injection layer; al of 120nm was vacuum-evaporated on the electron injection layer to form a cathode.

Examples 37 to 70: preparation of organic electroluminescent devices 37-70

The organic electroluminescent devices 37 to 70 were obtained by replacing compound 3 in the second hole transport layer of example 36 with compound 32, compound 41, compound 44, compound 48, compound 58, compound 78, compound 84, compound 91, compound 94, compound 95, compound 99, compound 109, compound 122, compound 131, compound 142, compound 147, compound 152, compound 155, compound 183, compound 184, compound 198, compound 199, compound 200, compound 223, compound 239, compound 245, compound 254, compound 263, compound 277, compound 326, compound 427, compound 469, compound 484 and compound 560, respectively, and the other steps being the same.

Comparative examples 4 to 6: preparation of comparative organic electroluminescent devices 4 to 6

The compound 3 in the second hole transport layer of example 36 was changed to R-1, R-3, R-4, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 4 to 6.

The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 36 to 70 of the present invention and comparative examples 4 to 6 are shown in table 2.

Table 2 light emission characteristic test data of organic electroluminescent device

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As can be seen from the results of table 2, when the aromatic amine derivative of the present invention is applied to an organic electroluminescent device as a second hole transport layer material, the performance of the device is significantly improved compared with comparative examples 4 to 6, and the aromatic amine derivative has the advantages of high luminous efficiency and long service life.

Example 71: preparation of organic electroluminescent device 71

ITO is used as an anode on the glass substrate; vacuum evaporation of 15nm NPB on anode: f4TCNQ (mass ratio 95%:5% mixed) forms a hole injection layer; vacuum evaporating NPB of 20nm on the hole injection layer to form a first hole transport layer; vacuum evaporating 10nm HT-2 on the first hole transport layer to form a second hole transport layer; forming a third hole transport layer by vacuum evaporation of 10nm of the compound 3 of the present invention on the second hole transport layer; vacuum evaporating 30nm BH-3:BD-3 (mass ratio 98%:2% mixture) on the third hole transport layer to form a light emitting layer; vacuum evaporating ET-1 of 30nm on the light-emitting layer: liq (mass ratio 1:1 mixture) forms an electron transport layer; vacuum evaporating LiF of 1.0nm on the electron transport layer to form an electron injection layer; al of 120nm was vacuum-evaporated on the electron injection layer to form a cathode.

Examples 72 to 105: preparation of organic electroluminescent devices 72-105

The organic electroluminescent devices 72 to 105 were obtained by replacing compound 3 in the third hole transport layer of example 71 with compound 32, compound 41, compound 44, compound 48, compound 58, compound 78, compound 84, compound 91, compound 94, compound 95, compound 99, compound 109, compound 122, compound 131, compound 142, compound 147, compound 152, compound 155, compound 183, compound 184, compound 198, compound 199, compound 200, compound 223, compound 239, compound 245, compound 254, compound 263, compound 277, compound 326, compound 427, compound 469, compound 484 and compound 560, respectively, and the other steps being the same.

Comparative examples 7 to 9: preparation of comparative organic electroluminescent devices 7 to 9

The compound 6 in the third hole transport layer of example 77 was changed to R-1, R-5, R-6, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 7 to 9.

The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 71 to 105 of the present invention and comparative examples 7 to 9 are shown in table 3.

Table 3 light emission characteristics test data of organic electroluminescent device

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As can be seen from the results of table 3, when the aromatic amine derivative of the present invention is applied to an organic electroluminescent device as a material for a third hole transport layer, the luminous efficiency and the service life of the device are improved as compared with comparative examples 7 to 9.

Example 106: preparation of organic electroluminescent device 106 (laminated organic electroluminescent device)

ITO is used as an anode on the glass substrate; vacuum evaporation of 15nm NPB on anode: f4TCNQ (97% by mass to 3% mixed) forms a hole injection layer; vacuum evaporating 35nm NPB on the hole injection layer to form a hole transport layer 1; forming a light-emitting layer 1 by vacuum evaporation of 25nm BH-1:BD-1 (96% by mass: 4% mixed) on the hole transport layer 1; vacuum evaporation of 20nm ET-1 on the light-emitting layer 1: liQ (mass ratio 1:1 mixture) forms an electron transport layer 1; vacuum evaporation of 10nm Bphen on electron transport layer 1: li (mass ratio 98%:2% mixed) forms an N-type charge generation layer; vacuum evaporating 10nm compound 3:HAT-CN (95% by mass: 5% mixed) on the N-type charge generation layer to form a P-type charge generation layer; vacuum evaporating 25nm NPB on the P-type charge generation layer to form a hole transport layer 2; forming a light-emitting layer 2 by vacuum evaporation of 25nm BH-1:BD-1 (96% by mass: 4% mixed) on the hole-transport layer 2; vacuum evaporation of 20nm ET-1 on the light-emitting layer 2: liQ (mass ratio 1:1 mixture) forms an electron transport layer 2; vacuum evaporation of 10nm EI-1 on electron transport layer 2: li (97% by mass to 3% by mass) forms an electron injection layer; and vacuum evaporating 110nm Al on the electron injection layer to form a cathode.

Examples 107 to 125: preparation of organic electroluminescent devices 107 to 125

The P-type charge generation layer of example 106 was changed to 32, 44, 48, 58, 84, 91, 94, 95, 99, 109, 131, 155, 184, 198, 239, 254, 263, 427, 469, respectively, and the other steps were the same, to obtain organic electroluminescent devices 107 to 125.

Comparative examples 10 to 11: preparation of comparative organic electroluminescent devices 10 to 11

The compound 3 in the P-type charge generation layer of example 106 was changed to R-7 and NPB, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 10 to 11.

The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 106 to 125 of the present invention and comparative examples 10 to 11 are shown in table 4.

Table 4 light emission characteristics test data of organic electroluminescent device

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As can be seen from the results of table 4, when the aromatic amine derivative of the present invention is applied to the P-type charge generation layer material of the organic electroluminescent device, the luminous efficiency and the service life of the organic electroluminescent device are greatly improved as compared with those of comparative examples 10 to 11, which indicates that the compound of the present invention has good technical effects when being used as the P-type charge generation layer material in the stacked OLED device.

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

Claims

1. An aromatic amine derivative is characterized by having a general formula shown in a structural formula 1,

the X is selected from O atoms and N (R _d);

The L ₃ is selected from a single bond or a group as shown below:

2. The aromatic amine derivative according to claim 1, wherein in the formula 1Any one selected from the following groups:

3. The aromatic amine derivative according to claim 1, wherein in the formula 1Any one selected from the following groups:

4. The aromatic amine derivative according to claim 1, wherein in the formula 1Any one selected from the following groups:

5. The aromatic amine derivative according to claim 1, wherein L ₁、L₂ is independently selected from a single bond or any one of the following groups:

6. The aromatic amine derivative according to claim 1, wherein L ₃ is selected from a single bond or any one of the following groups:

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7. The aromatic amine derivative according to claim 1, wherein the aromatic amine derivative represented by formula 1 is selected from any one of the following chemical structures:

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8. An organic electroluminescent device comprising: a first electrode, a second electrode arranged opposite to the first electrode, and an organic layer positioned between the first electrode and the second electrode or outside one or more of the first electrode and the second electrode, wherein the organic layer contains any one or a combination of at least two of the aromatic amine derivatives according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, wherein the organic layer comprises a hole transport region, a light emitting layer, an electron transport region, and a capping layer, wherein at least one layer of the hole transport region contains any one or a combination of at least two of the aromatic amine derivatives according to any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 8, wherein the organic layer comprises a hole transport region, two or more light emitting layers, an electron transport region, and a capping layer, and wherein an N-type charge generation layer and a P-type charge generation layer are provided between each light emitting layer, wherein the P-type charge generation layer contains any one or a combination of at least two of the aromatic amine derivatives according to any one of claims 1 to 7.