CN117377338A

CN117377338A - Organic electroluminescent device

Info

Publication number: CN117377338A
Application number: CN202311321525.0A
Authority: CN
Inventors: 董秀芹; 陆影; 周雯庭; 刘喜庆
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-10-12
Filing date: 2023-10-12
Publication date: 2024-01-09

Abstract

The invention provides an organic electroluminescent device, and particularly relates to the technical field of organic electroluminescent. The organic electroluminescent device provided by the invention is characterized in that a hole transmission area containing a structure shown in a formula I or a formula II is matched with an electron transmission area containing a structure shown in a formula III, so that the transmission balance of holes/electrons in the device is improved, the energy consumption in the transmission process is reduced, the recombination probability of the holes and electrons in a luminescent layer is increased, the generation of Joule heat in the device is reduced, the luminous efficiency of the organic electroluminescent device is further improved, and the service life of the device is prolonged.

Description

Organic electroluminescent device

Technical Field

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

Background

An Organic Light-Emitting Diode (OLED). Compared with the traditional Liquid Crystal Display (LCD), the OLED display technology has the advantages of self-luminescence, wide viewing angle, high resolution, energy conservation, high response speed, stable color, strong environmental adaptability, no radiation, light weight, thin thickness and the like, and has wide application prospect in new generation display and illumination products.

The working principle of the organic electroluminescent device is that under the action of an external electric field, holes and electrons are respectively injected into an organic layer from an anode and a cathode, enter a luminescent region through a hole transmission region and an electron transmission region, and are combined to generate excitons, energy is released, the excitons migrate under the action of the electric field, the energy is transferred to luminescent substances in the luminescent region, electrons in molecules of the luminescent substances are excited to transit from a ground state to an excited state, and when the electrons return to the ground state from the excited state, the energy is released in a light form, so that a luminescent phenomenon is generated. The classical sandwich structure of the organic electroluminescent device is composed of a cathode, an anode and an organic layer, wherein the organic functional layer mainly comprises: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emitting layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) and a capping layer (CPL).

With the continuous development of OLED products, the requirements on the performances such as luminous efficiency, service life and the like of the OLED products are higher and higher. However, in order to obtain an OLED with high light-emitting efficiency and long service life, it is necessary to obtain a material with balanced hole and electron transport, and control the hole and electron transport in the light-emitting layer to be effectively combined, and it is critical that the energy levels between the functional layers and the properties of the material itself are matched with each other, so that designing an organic material with good thermal stability, suitable HOMO energy level, good film forming property, and capability of achieving maximum combination of the hole and electron in the light-emitting layer is an urgent problem to be solved for improving the service performance of an organic electroluminescent device.

Disclosure of Invention

In order to improve the luminous efficiency of the organic electroluminescent device and prolong the service life of the device, the invention provides the organic electroluminescent device. Specifically, the technical scheme of the invention is as follows:

the invention provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a hole transmission region, a luminescent layer, an electron transmission region and a covering layer, the hole transmission region comprises any one of structures shown in a formula I or a formula II, and the electron transmission region comprises a structure shown in a formula III;

in formula I, the Ar ₁ 、Ar ₂ Are the same or different from each other and are selected from any one of the groups shown in the formula I-1 and the formula I-2;

the R is ₃ 、R _a 、R _b Are identical or different from each other, and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted silyl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group, or R _a 、R _b May be linked to each other to form a substituted or unsubstituted ring;

The m is ₁ Selected from 0, 1, 2, 3, 4 or 5, said m ₂ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, when two or more R's are present ₃ When two or more R' s ₃ Identical or different from each other, or adjacent two R' s ₃ May be linked to each other to form a substituted or unsubstituted ring;

the Ar is as follows ₃ Any one selected from a substituted or unsubstituted C1 to C12 alkyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 aromatic ring, and a C3 to C30 aliphatic ring condensed ring group;

said L, L ₁ -L ₃ Are identical or different from each other and are selected from single bonds, substituted or unsubstituted arylene groups of C6-C30, divalent substituted or unsubstituted aromatic rings of C6-C30 and aliphatic rings of C3-C30Any one of condensed ring groups of (2);

the R is ₁ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;

Said n ₁ Selected from 0, 1, 2, 3, 4, 5, 6 or 7; when two or more R's are present ₁ When two or more R' s ₁ Identical or different from each other, or adjacent two R' s ₁ May be linked to each other to form a substituted or unsubstituted ring;

in formula II, the Ar _a -Ar _d Are the same or different from each other and selected from any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted tetrahydronaphthyl group, a substituted or unsubstituted dihydronaphthyl group, a substituted or unsubstituted indanyl group, a substituted or unsubstituted indenyl group, and combinations thereof;

the L is ₀ Any one selected from the group consisting of a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted tetrahydronaphthylene group, a substituted or unsubstituted dihydronaphthylene group, a substituted or unsubstituted indanylene group, a substituted or unsubstituted indenylene group, and combinations thereof;

the L is _a -L _d Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted arylene of C6-C30, bivalent substituted or unsubstituted aromatic ring of C6-C30 and condensed ring group of aliphatic ring of C3-C30;

In formula III, the Ar ₄ -Ar ₆ Is the same or different from each other and is selected from any one of substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C2-C30, substituted or unsubstituted aromatic ring of C6-C30 and condensed ring group of aliphatic ring of C3-C30;

the saidL ₄ -L ₆ Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, bivalent substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group and combination thereof;

said x, equal to or different from each other, are chosen from CH or N atoms and at least one is chosen from N atoms, said x being chosen from C atoms when they are bonded to other groups;

wherein the Ar is ₄ 、Ar ₅ 、Ar ₆ 、L ₄ 、L ₅ 、L ₆ At least one of which is substituted by one or more-Si (R) ₄ ) ₃ Substitution;

the R is ₂ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted silyl, and substituted or unsubstituted C2-C30 heteroaryl;

The R is ₄ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted silyl, and substituted or unsubstituted C2-C30 heteroaryl;

said n ₂ Selected from 0, 1, 2 or 3, when two or more R's are present ₂ When two or more R' s ₂ The same as or different from each other.

The beneficial effects are that: the hole transmission region of the organic electroluminescent device provided by the invention comprises any one of structures shown in a formula I or a formula II, and the electron transmission region comprises a structure shown in a formula III, so that the hole transmission region and the electron transmission region can cooperatively and efficiently transmit holes/electrons, the recombination efficiency of excitons is increased, the organic electroluminescent device has proper HOMO energy level and good thermal stability, the energy barrier of the holes/electrons in the transmission process is greatly reduced, the balance of the holes and the electrons in the transmission process is increased, the luminous efficiency of the device is further improved, and the service life of the device is prolonged.

Detailed Description

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

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

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

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

In this specification, when 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 indicate->Can representCan represent And so on.

In the present specification, when substitutedWhere a bond between two or more rings is a base or a linking site, it is meant that it may be attached to either of the two or more rings, in particular to either of the corresponding selectable sites of the rings. For example, the number of the cells to be processed,can indicate-> Can indicate->And so on.

The halogen refers to fluorine, chlorine, bromine and iodine.

Alkyl according to the invention is understood to mean a monovalent radical obtained by removing one hydrogen atom from an alkane molecule, which may be a straight-chain alkyl radical or a branched alkyl radical, preferably having from 1 to 12 carbon atoms, more preferably having from 1 to 8 carbon atoms, particularly preferably having from 1 to 6 carbon atoms. Alkyl groups may be substituted or unsubstituted. Specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but are not limited thereto.

Alkenyl groups according to the present invention means monovalent groups of an olefin molecule from which one hydrogen atom is removed, preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, and examples may include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and the like.

Cycloalkyl according to the present invention means a monovalent group obtained by removing one hydrogen atom from a cyclic alkane molecule, preferably having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted. The cycloalkyl group includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.

Aryl according to the invention is understood to mean a monovalent radical obtained by removing one hydrogen atom from the aromatic nucleus of an aromatic compound molecule, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl, preferably having from 6 to 30 carbon atoms, more preferably from 6 to 18 carbon atoms, particularly preferably from 6 to 12 carbon atoms. Aryl groups may be substituted or unsubstituted. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, for example, phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, tetrabiphenyl, etc., but is not limited thereto; the condensed ring aryl group means an aryl group having two or more aromatic rings in the molecule and condensed with each other by sharing two adjacent carbon atoms, for example, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, Radicals, triphenylene radicals, fluoranthenyl radicals, fluorenyl radicals, spirobifluorenyl radicals, and the like, but are not limited thereto.

Heteroaryl according to the present invention refers to the generic term for groups in which one or more of the aromatic nucleus carbon atoms in the aryl group is replaced by a heteroatom, including but not limited to O, S, N, si or P atoms, preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 3 to 12 carbon atoms. The attachment site of the heteroaryl group may be on a ring-forming carbon atom or on a ring-forming heteroatom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a fused ring heteroaryl group. Heteroaryl groups may be substituted or unsubstituted. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, etc., but is not limited thereto; the fused ring heteroaryl group includes quinolinyl, isoquinolinyl, benzoquinolinyl, benzoisoquinolinyl, quinazolinyl, quinoxalinyl, benzoquinazolinyl, benzoquinoxalinyl, phenanthroline, naphthyridinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, N-heterobenzoxazolyl, N-heterobenzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, dibenzooxazolyl, dibenzoimidazolyl, dibenzozolyl, carbazolyl, benzocarbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, spirofluorene oxaanthracenyl, spirofluorene thioanthracenyl, and the like, but is not limited thereto.

The aliphatic ring according to the present invention is a cyclic hydrocarbon having aliphatic properties, and the molecule contains a closed carbon ring, preferably 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms, and still more preferably 3 to 7 carbon atoms. Which may form mono-or polycyclic hydrocarbons and may be fully unsaturated or partially unsaturated. The aliphatic ring may be substituted or unsubstituted. Specific examples may include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, 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-like structure.

The fused ring of an aromatic ring and an aliphatic ring in the present invention means a ring having one or more aromatic rings and having one or more aliphatic rings fused to each other by sharing two adjacent carbon atoms, the aromatic ring preferably has 6 to 30 carbon atoms, more preferably has 6 to 18 carbon atoms, most preferably has 6 to 12 carbon atoms, and the aliphatic ring preferably has 3 to 30 carbon atoms, more preferably has 3 to 18 carbon atoms, more preferably has 3 to 12 carbon atoms, and most preferably has 3 to 7 carbon atoms. The fused ring of the aromatic ring and the aliphatic ring may be substituted or unsubstituted. Examples include, but are not limited to, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclobutene, benzocyclopentene, benzocyclohexene, benzocycloheptene, naphthocyclopropane, naphthocyclobutane, naphthocyclopentane, naphthocyclohexene, naphthocyclopentene, naphthocyclohexene, and the like.

As used herein, "substituted or unsubstituted silyl" refers to-Si (R) _k ) ₃ A group wherein each R _k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused ring groups of substituted or unsubstituted C3-C30 alicyclic and C6-C30 aromatic rings, fused ring groups of substituted or unsubstituted C3-C30 alicyclic and C2-C30 heteroaromatic rings. Preferably, each R _k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl. The number of carbon atoms of the alkyl group is preferably 1 to 20, preferably 1 to 15, more preferably 1 to 10, and most preferably 1 to 8. The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, preferably 3 to 15, more preferably 3 to 10, and most preferably 3 to 7. The number of carbon atoms of the aryl group is preferably 6 to 20, preferably 6 to 13, more preferably 6 to 12, and most preferably 6 to 10. Preferably, each R _k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl. Preferred substituted silyl group concrete packageIncluding, but not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tri-t-butylsilyl, t-butyldimethylsilyl, ethyldimethylsilyl, isopropyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like. The above-mentioned substituted silyl group is preferably trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, triphenylsilyl group, but is not limited thereto.

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

The heteroarylene group according to the present invention is a divalent group obtained by removing two hydrogen atoms from the nuclear carbon of an aromatic heterocycle comprising carbon and a heteroatom. These are, in addition to the divalent radicals, in each case, suitable for the description of heteroaryl radicals given above.

The fused ring group of the divalent aromatic ring and the aliphatic ring in the present invention means that there are two linked positions, i.e., a divalent group, on the fused ring group of the aromatic ring and the aliphatic ring. In addition to the divalent groups, the above description of the condensed ring groups of the aromatic ring and the aliphatic ring may be applied.

"unsubstituted" in "substituted or unsubstituted" as used herein means that the hydrogen atom on the group is not substituted with any substituent; "substituted" means that at least one hydrogen atom on the group is replaced with a substituent, and the position of substitution is not limited. When a plurality of hydrogens are substituted with a plurality of substituents, the plurality of substituents may be the same or different.

The substituents mentioned in the "substituted or unsubstituted" in the present invention may be the same or different from each other and are selected from deuterium, cyano, nitro, trifluoromethyl, halogen atom, substituted or unsubstituted C1-C12 alkyl group, substituted or unsubstituted C2-C12 alkenyl group, substituted or unsubstituted C3-C12 cycloalkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted C2-C12 heterocycloalkyl group, substituted or unsubstituted C6-C12 30 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, any one of a condensed ring group of a substituted or unsubstituted C6 to C30 aromatic ring and a C3 to C30 aliphatic ring, preferably deuterium, cyano group, halogen atom, trifluoromethyl group, C1 to C12 alkyl group, C3 to C12 cycloalkyl group, silyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano group, trifluoromethyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group, norbornyl group, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, triphenylsilyl group, phenyl group, biphenyl group, terphenyl group, tolyl group, pentadeuterated phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylyl group,A group, perylene group, fluoranthenyl group, fluorenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, spirofluorenyl group, carbazolyl group, 9-phenylcarbazolyl group, 9' -spirobifluorenyl group, benzocyclopropanyl group, benzocyclobutanyl group, benzocyclopentanyl group, benzocyclohexenyl group, benzocycloheptanyl group, benzocyclobutenyl group, benzocyclopentenyl group, benzocyclohexenyl group, benzocycloheptenyl group, pyrrolyl group, furyl group, thienyl group, benzofuryl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, oxazolyl group, thiazolyl group, imidazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, benzimidazolyl group, quinolinyl group, isoquinolinyl group, quinoxalinyl group, quinazolinyl group, phenothiazinyl group, phenoxazinyl group, acridinyl group, and the like, but not limited thereto; or when two or more of the substituents are present, two or more substituents may be the same or different from each other, or adjacent substituents may be bonded to form a ring.

In this specification, the "adjacent two groups are linked to form a ring" means that a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle is formed by bonding adjacent groups to each other and optionally aromatizing. 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 specification, the ring formed by the connection may be an aromatic ring or a non-aromatic ring, and may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring, a condensed ring, or the like, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, adamantane, norbornane, benzene, naphthalene, phenanthrene, triphenylene, pyridine, pyrimidine, quinoline, isoquinoline, quinazoline, quinoxaline, fluorene, dibenzofuran, dibenzothiophene, carbazole, or the like, but is not limited thereto.

The term "at least one" as used herein includes one, two, three, four or more.

The term "one or more" in the present invention includes one, two, three, four, five, six, seven, eight, nine, ten or more, where permitted.

In the organic electroluminescent device according to the present invention, each functional layer may be formed of a single layer or two or more thin films, and each thin film may be formed of one material or two or more materials, however, the structure of the organic electroluminescent device is not limited thereto.

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 invention provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a hole transmission region, a luminescent layer, an electron transmission region and a covering layer, the hole transmission region comprises any one of structures shown in a formula I or a formula II, and the electron transmission region comprises a structure shown in a formula III.

Next, the constitution of an organic electroluminescent device including either the structure shown in formula I or formula II as a hole transport region material, and the structure shown in formula III as an electron transport region material will be described in more detail.

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 anode material of the present invention preferably has a high function and improves hole injection efficiency. Anode materials useful in the present invention are selected from the following: indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and tin oxide (SnO) ₂ ) Zinc oxide (ZnO) or any combination thereof, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof. The anode may have a single-layer structure or a multi-layer structure including two or more layers, for example, the anode may have a single-layer structure of Al or a three-layer structure of ITO/Ag/ITO, but is not limited thereto.

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

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

Preferably, the hole transport region according to the present invention includes a hole injection layer and a hole transport layer;

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

preferably, the hole transport region according to the present invention includes a hole injection layer;

preferably, the hole transport region according to the present invention includes an electron blocking layer;

preferably, the hole transport region according to the present invention includes a hole transport layer;

preferably, the hole transport region according to the present invention includes at least one of a first hole transport layer and a second hole transport layer;

preferably, the hole transport layer of the present invention is located between the anode and the light emitting layer;

preferably, the hole transport layer of the present invention is located between the hole injection layer and the light emitting layer.

The hole transport region of the present invention includes any one of the structures of formula I or formula II,

said L, L ₁ -L ₃ Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted arylene of C6-C30, bivalent substituted or unsubstituted aromatic ring of C6-C30 and condensed ring group of aliphatic ring of C3-C30;

the L is ₀ Selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted tetrahydronaphthylene, substituted or unsubstituted dihydronaphthylene, substituted or unsubstituted indanylene, substituted or unsubstitutedA substituted indenylene, and combinations thereof;

the L is _a -L _d Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted arylene of C6-C30, bivalent substituted or unsubstituted aromatic ring of C6-C30 and condensed ring group of aliphatic ring of C3-C30.

Preferably, the Ar ₁ 、Ar ₂ Are the same or different from each other, and are selected from any one of the structures shown below;

the R is ₃ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group shown as the following which is substituted or unsubstituted by one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, triphenylsilyl, ethyldimethylsilyl, t-butyldimethylsilyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptyl, benzocyclopentenyl, or benzocyclohexenyl;

the a ₁ Selected from 0, 1, 2, 3, 4 or 5, said a ₂ Selected from 0, 1, 2, 3 or 4, said a ₃ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said a ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said a ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said a ₆ Selected from 0, 1, 2 or 3, said a ₇ Selected from 0, 1,2. 3, 4, 5 or 6, said a ₈ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said a ₉ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said a ₁₀ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, said a ₁₁ Selected from 0, 1 or 2.

Preferably, the Ar ₃ Selected from any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C6 alkyl, silyl groups: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, benzocyclopropenyl, benzocyclobutanyl, benzocyclopentenyl, benzocyclohexenyl, benzothienyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl or naphthyridinyl.

Preferably, the Ar ₃ Any one of methyl, ethyl, isopropyl, tertiary butyl, deuterated methyl, deuterated isopropyl, deuterated tertiary butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane or a group shown below;

The R is ₁₀ Are the same or different from each other and are selected from hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, deuterated methyl, deuterated isopropyl, deuterated tert-butyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl, triphenylsilyl;

said g ₁ Selected from 0, 1, 2, 3, 4 or 5, said g ₂ Selected from 0, 1, 2, 3 or 4, said g ₃ Selected from 0, 1, 2 or 3, said g ₄ Selected from 0, 1 or 2, said g ₅ Selected from 0, 1, 2, 3, 4, 5 or 6, said g ₆ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said g ₇ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

Preferably, the L, L ₁ -L ₃ Are the same or different from each other, and are selected from any one of single bonds or groups shown below;

the R is ₁₁ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group shown as the following which is substituted or unsubstituted by one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, benzocyclopentyl, benzocyclohexenyl or benzocyclohexenyl;

The h is ₁ Selected from 0, 1, 2, 3 or 4, said h ₂ Selected from 0, 1, 2, 3, 4, 5 or 6, said h ₃ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said h ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Preferably, said R ₁ Selected from hydrogen, deuterium, or any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, benzocyclohexenyl, benzofuranyl, benzothienyl, pyridinyl, pyrimidinyl, triazinyl, quinolinylIsoquinolinyl, quinazolinyl, quinoxalinyl or naphthyridinyl.

Preferably, the Ar _a -Ar _d Are the same or different from each other, and are selected from any one of the structures shown below;

the R is _c 、R _d Identical to or different from each other, selected from hydrogen, deuterium, halogen, cyano or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C6 alkyl, silyl groups: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, benzocycloheptyl, benzocyclopentenyl, benzofuranyl or benzothienyl, or R _c 、R _d May be linked to each other to form a substituted or unsubstituted ring;

the R is ₅ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group shown as the following which is substituted or unsubstituted by one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, triphenylsilyl, ethyldimethylsilyl, t-butyldimethylsilyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptyl, benzocyclopentenyl, or benzocyclohexenyl;

said b ₁ Selected from 0, 1, 2, 3, 4 or 5, said b ₂ Selected from 0, 1, 2,3 or 4, said b ₃ Selected from 0, 1, 2 or 3, said b ₄ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said b ₅ Selected from 0, 1, 2, 3, 4, 5 or 6, said b ₆ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, when two or more R's are present ₅ When two or more R' s ₅ Identical or different from each other, or adjacent two R ₅ May be linked to each other to form a substituted or unsubstituted ring.

/>

preferably, the L ₀ Selected from any one of the structures shown below;

the R is ₆ Identical to or different from each other, selected from hydrogen, deuterium, or any one of the following groups substituted or unsubstituted by one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, triphenylsilyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentanyl or benzocyclohexenyl;

the c ₁ Selected from 0, 1, 2, 3 or 4, said c ₂ Selected from 0, 1, 2 or 3, said c ₃ Selected from 0, 1 or 2, said c ₄ Selected from 0, 1, 2, 3, 4, 5 or 6, said c ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

Preferably, the L _a -L _d Identical or different from each other, selected from single bonds or from one or more R ₁₂ Substituted or unsubstituted: any one of phenylene, biphenylene, terphenylene, tetra-biphenylene, naphthylene, benzocyclopentylene, benzocyclohexenylene, benzocyclopentylene, or benzocyclohexenylene, and combinations thereof;

the R is ₁₂ Any one of the following groups selected from hydrogen, deuterium, cyano, halogen, trifluoromethyl, substituted or unsubstituted: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-tert-butylsilyl or triphenylsilyl, when two or more R's are present ₁₂ When two or more R' s ₁₂ The same as or different from each other.

Preferably, the hole transport region is selected from any one of the structures shown below;

/>

the hole transport regions of the present invention are exemplified above as comprising specific structural forms of the compounds of formula I or formula II, but the present invention is not limited to these chemical structures, and substituents are included as defined above, even when the structures of formula I or formula II are used as bases.

The hole injection layer material of the present invention is preferably a material having a good hole accepting ability. Specific examples of the hole injection layer material that can be used in the present invention may include metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, etc., phthalocyanine compounds, biphenylamine compounds, phenazine compounds, etc., such as copper phthalocyanine (CuPc), titanylphthalocyanine, N ' -diphenyl-N, N ' -bis- [4- (N, N-diphenylamine) phenyl ] benzidine (npb), N ' -tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), and bisquinoxalino [2,3-a:2',3' -c ] phenazine (HATNA), 4',4 "-tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN), 4',4" -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but are not limited thereto. Or a structure shown as a formula I or a formula II.

The hole transport layer material according to the present invention is preferably a material having high hole mobility. Can be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, stilbene derivatives, hexanitrile hexaazabenzophenanthrene compounds, quinacridone compounds, anthraquinone compounds, polyaniline, polythiophene, polyvinylcarbazole, and the like. Examples of the hole transport layer material include, but are not limited to, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), N '-tetrakis (3-methylphenyl) -3,3' -dimethylbiphenyl diamine (HMTPD), and the like. Or a structure shown as a formula I or a formula II.

The electron blocking layer material according to the present invention preferably uses a material having a property of blocking electrons from passing through the light emitting layer, and specific examples may include triarylamine derivatives, spirofluorene derivatives, furan derivatives, etc., 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-bis ([ 1,1' -biphenyl ] -4-yl) -3'- (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine, and the like, but are not limited thereto. Or a structure shown as a formula I or a formula II.

The luminescent layer material comprises a host material AND a doping material, AND the luminescent layer host material can be selected from 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4 '-tris (carbazole-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (alpha-AND), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4', 1':4', 1' -tetrabiphenyl]-4,4' -diamine (4 PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), etc. In addition to the above materials and combinations thereof, the light emitting layer host material may include other known materials suitable for a light emitting layer, and the like, but is not limited thereto. The light-emitting layer doping material of the present invention is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. The light-emitting layer doping material can be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -di [4- (diphenylamino) styryl) ]Biphenyl (BDAVBi), 4' -di [4- (di-p-tolylamino) styryl]Diphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp 2), bis (4, 6-difluorophenylpyridine-C2, N) iridium picolinate (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) ₂ (acac)), 9, 10-bis [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq) ₃ ) Ir (piq) iridium bis (1-phenylisoquinoline) (acetylacetonate) ₂ (acac)) and the like, but is not limited thereto.

The doping ratio of the host material and the guest material in the light-emitting layer according to the present invention is determined according to the materials used. The amount of the dopant is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, still more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

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

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

Preferably, the electron transport region according to the present invention includes an electron injection layer and an electron transport layer;

preferably, the electron transport region of the present invention includes an electron injection layer and a hole blocking layer;

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

preferably, the electron transport region according to the present invention includes an electron injection layer;

preferably, the electron transport region according to the present invention includes an electron transport layer;

preferably, the electron transport region according to the present invention includes a hole blocking layer.

The electron transport region comprises a structure shown in a formula III;

the L is ₄ -L ₆ Are the same or different from each other, and are selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene, bivalent substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring condensed ring group and combination thereof;

Preferably, x is the same or different from each other and is selected from CH or N atoms, and at least one selected from N atoms means that one, two or three selected from N atoms in x.

Preferably, the Ar ₄ 、Ar ₅ 、Ar ₆ 、L ₄ 、L ₅ 、L ₆ At least one group of (C) is substituted with one or more Si (R ₄ ) ₃ Substitution, comprising: ar (Ar) ₄ -Ar ₆ 、L ₄ -L ₆ Is bonded to one or more Si (R ₄ ) ₃ Substituted, particularly Ar ₄ 、Ar ₅ 、Ar ₆ 、L ₄ 、L ₅ Or L ₆ Is formed by one or more Si (R ₄ ) ₃ Substitution; ar (Ar) ₄ -Ar ₆ 、L ₄ -L ₆ Each of the two groups in (2) is substituted with one or more Si (R ₄ ) ₃ Substituted, particularly Ar ₄ And Ar is a group ₅ 、Ar ₄ And Ar is a group ₆ 、Ar ₅ And Ar is a group ₆ 、L ₄ And L ₅ 、L ₄ And L ₆ 、L ₅ And L ₆ 、Ar ₄ And L ₄ 、Ar ₅ And L ₅ 、Ar ₆ And L ₆ 、Ar ₄ And L ₅ 、Ar ₄ And L ₆ 、Ar ₅ And L ₄ 、Ar ₅ And L ₆ 、Ar ₆ And L ₄ 、Ar ₆ And L ₅ Each group of (C) is substituted with one or more Si (R ₄ ) ₃ Substitution; ar (Ar) ₄ -Ar ₆ 、L ₄ -L ₆ Each of the three groups in (a) is substituted with one or more Si (R) ₄ ) ₃ Substituted, particularly Ar ₄ 、Ar ₅ And Ar is a group ₆ ，L ₄ 、L ₅ And L ₆ ，Ar ₄ 、Ar ₅ And L ₄ ，Ar ₄ 、Ar ₅ And L ₅ ，Ar ₄ 、Ar ₅ And L ₆ ，Ar ₄ 、Ar ₆ And L ₄ ，Ar ₄ 、Ar ₆ And L ₅ ，Ar ₄ 、Ar ₆ And L ₆ ，Ar ₆ 、Ar ₅ And L ₄ ，Ar ₆ 、Ar ₅ And L ₅ ，Ar ₆ 、Ar ₅ And L ₆ ，L ₄ 、L ₅ And Ar is a group ₄ ，L ₄ 、L ₅ And Ar is a group ₅ ，L ₄ 、L ₅ And Ar is a group ₆ ，L ₄ 、L ₆ And Ar is a group ₄ ，L ₄ 、L ₆ And Ar is a group ₅ ，L ₄ 、L ₆ And Ar is a group ₆ ，L ₅ 、L ₆ And Ar is a group ₄ ，L ₅ 、L ₆ And Ar is a group ₅ ，L ₅ 、L ₆ And Ar is a group ₆ Each group of (C) is substituted with one or more Si (R ₄ ) ₃ Substitution; ar (Ar) ₄ -Ar ₆ 、L ₄ -L ₆ Each of the four groups in (2) is substituted with one or more Si (R) ₄ ) ₃ Substituted, particularly Ar ₄ 、Ar ₅ 、Ar ₆ And L ₄ ，Ar ₄ 、Ar ₅ 、Ar ₆ And L ₅ ，Ar ₄ 、Ar ₅ 、Ar ₆ And L ₆ ，L ₄ 、L ₅ 、L ₆ And Ar is a group ₄ ，L ₄ 、L ₅ 、L ₆ And Ar is a group ₅ ，L ₄ 、L ₅ 、L ₆ And Ar is a group ₆ ，Ar ₄ 、Ar ₅ 、L ₅ And L ₄ ，Ar ₄ 、Ar ₆ 、L ₆ And L ₄ ，Ar ₆ 、Ar ₅ 、L ₅ And L ₆ Each group of (C) is substituted with one or more Si (R ₄ ) ₃ Substitution; ar (Ar) ₄ -Ar ₆ 、L ₄ -L ₆ Is substituted with one or more Si (R ₄ ) ₃ Substituted, particularly Ar ₄ 、Ar ₅ 、L ₅ 、L ₄ And L ₆ ，Ar ₄ 、Ar ₅ 、L ₅ 、L ₄ And Ar is a group ₆ ，Ar ₄ 、Ar ₆ 、L ₆ 、L ₄ And L ₅ ，Ar ₄ 、Ar ₆ 、L ₆ 、L ₄ And Ar is a group ₅ ，Ar ₅ 、Ar ₆ 、L ₆ 、L ₅ And L ₄ ，Ar ₅ 、Ar ₆ 、L ₆ 、L ₅ And Ar is a group ₄ Each group of (C) is substituted with one or more Si (R ₄ ) ₃ Substitution; ar (Ar) ₄ -Ar ₆ 、L ₄ -L ₆ Is composed of one or more Si (R ₄ ) ₃ Substituted, particularly Ar ₄ 、Ar ₅ 、Ar ₆ 、L ₄ 、L ₅ And L ₆ Each group of (B) is substituted with one or more-Si (R) ₄ ) ₃ And (3) substitution.

Preferably, said R ₂ Selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, hydroxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylyl, trimethylsilyl, triethylsilyl, triisopropylsilylAny one of tri-t-butylsilyl, triphenylsilyl, pyridine, pyrimidine, quinoline, isoquinoline, quinazoline, quinoxaline, naphthyridine;

preferably, the-Si (R ₄ ) ₃ Selected from any one of the structures shown below;

preferably, the Ar ₄ -Ar ₆ Are the same or different from each other, and are selected from any one of the structures shown below;

said v being identical to or different from each other and being selected from CH or N atoms and at least one of them being selected from N atoms, said v being selected from C atoms when bonded to other groups;

said T, Q, t ₁ Are identical or different from each other and are selected from O, S, C (R _x R _y )、N(R _z ) Any one of them;

The t is ₂ Selected from CH or N atoms;

the R is _x 、R _y Are identical or different from each other and are selected from hydrogen, deuterium, halogen, cyano or alkyl groups which are substituted by one or more deuterium, C1-C6, -Si (R) ₄ ) ₃ A substituted or unsubstituted group of any of the following: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, and the like terphenyl, naphthyl, anthryl, phenanthryl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, benzocyclohexenyl, benzoFuryl or benzothienyl, or R _x 、R _y May be linked to each other to form a substituted or unsubstituted ring;

the R is _z Selected from the group consisting of alkyl groups with one or more deuterium, C1-C6, -Si (R) ₄ ) ₃ A substituted or unsubstituted group of any of the following: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, benzocyclohexenyl, benzofuranyl, or benzothienyl;

the R is ₇ Are identical or different from each other and are selected from hydrogen, deuterium, -Si (R) ₄ ) ₃ Or any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, benzocyclopropanyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, benzocyclohexenyl, benzofuranyl, benzothienyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or naphthyridinyl;

said d ₁ Selected from 0, 1, 2, 3, 4 or 5, said d ₂ Selected from 0, 1, 2, 3 or 4, said d ₃ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said d ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said d ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said d ₆ Selected from 0, 1, 2, 3, 4, 5 or 6, said d ₇ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said d ₈ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said d ₉ Selected from 0, 1, 2 or 3, said d ₁₀ Selected from 0, 1 or 2.

Preferably, said R ₇ Selected from-Si (R) ₄ ) ₃ The method comprises the steps of carrying out a first treatment on the surface of the More preferably, said R ₇ One, two or three of them are selected from-Si (R ₄ ) ₃ 。

/>

the t is ₂ Selected from CH or N atoms;

the R is _x 、R _y Are identical or different from each other and are selected from hydrogen, deuterium, halogen, cyano or alkyl groups which are substituted by one or more deuterium, C1-C6, -Si (R) ₄ ) ₃ A substituted or unsubstituted group of any of the following: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, benzocycloheptyl, benzocycloalkenyl, benzofuranyl, or benzothienyl;

the R is _z Selected from the group consisting of alkyl groups with one or more deuterium, C1-C6, -Si (R) ₄ ) ₃ Substituted or unsubstituted, e.g.Any one of the following groups: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, benzocyclohexenyl, benzofuranyl, or benzothienyl;

The R is _x 、R _y Can be connected with each other to form any one of the following ring groups,

/>

the R is ₈ Any one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 heteroaryl;

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

Preferably, the L ₄ -L ₆ Are the same or different from each other, and are selected from any one of single bonds or structures shown below and combinations thereof;

the R is ₉ Are identical or different from each other and are selected from hydrogen, deuterium, -Si (R) ₄ ) ₃ Or by one or moreDeuterium, C1-C6 alkyl substituted or unsubstituted any one of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, benzocyclopentyl, benzocyclohexenyl, benzocycloheptyl, benzofuranyl or benzothienyl;

Said f ₁ Selected from 0, 1, 2, 3 or 4, said f ₂ Selected from 0, 1, 2 or 3, said f ₃ Selected from 0, 1 or 2, said f ₄ Selected from 0, 1, 2, 3, 4 or 5, said f ₅ Selected from 0, 1, 2, 3, 4, 5 or 6, said f ₆ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said f ₇ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Preferably, said R ₉ Selected from-Si (R) ₄ ) ₃ The method comprises the steps of carrying out a first treatment on the surface of the More preferably, said R ₉ One, two or three of them are selected from-Si (R ₄ ) ₃ 。

Preferably, the electron transport region is selected from any one of the structures shown below;

/>

the electron transport regions of the present invention are exemplified above as including some specific structural forms of the compounds of formula III, but the present invention is not limited to these chemical structures, and substituents are included as defined above, even when the structures of formula III are used as bases.

The hole blocking layer according to the present invention preferably uses a material having a strong hole blocking ability and a suitable HOMO/LUMO energy level. The hole blocking layer material can be selected from any one or more of the following structures: phenanthroline derivatives, rare earth derivatives, imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, azabenzene derivatives, anthrone derivatives, and the like, but are not limited thereto; or a structure represented by formula III according to the present invention.

The electron transport layer material of the present invention is preferably a material having high electron mobility. Can be selected from any one or more of the following structures: 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), tris (8-hydroxyquinoline) aluminum (III) (Alq 3), 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-t-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like, but are not limited thereto; or a structure represented by formula III according to the present invention.

The electron injection layer material of the present invention is preferably a material having a small potential barrier difference from a material of an adjacent organic layer, and specific examples may include: alkali metal compounds (for example, lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, 8-hydroxyquinoline cesium, 8-hydroxyquinoline aluminum), organic metal salts (metal acetate, metal benzoate, or metal stearate), molybdenum trioxide, metal aluminum, and the like, but are not limited thereto; or a structure represented by formula III according to the present invention.

The cathode material according to the present invention preferably uses a material having a low work function that can promote electron injection into the organic layer to lower the electron injection barrier. Can be selected from any one or more of the following materials: ag. Mg, cu, al, pt, pd, au, ni, nd, ir, cr, li, ca, liF/Ca, liF/Al, mo, ti, compounds including them or mixtures thereof (e.g., mixtures of Ag and Mg), but are not limited thereto.

The coating layer according to the present invention is provided outside either one of the anode and the cathode, and preferably a material capable of improving the optical coupling efficiency inside the device is used. Can be selected from any one or more of the following structures: aryl amine derivatives, biscarbazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, triazole derivatives, benzofuran derivatives, diamine derivatives, porphyrin derivatives, phthalocyanine derivatives, and the like, but are not limited thereto.

The organic electroluminescent device according to the present invention may further include a substrate, and the substrate according to the present invention preferably uses a material that does not change when forming electrodes and other functional layers, and specific examples of the substrate material that can be used in the present invention may include glass, quartz, plastic, polymer film, silicon, etc., but are not limited thereto. The substrate may remain in a light emitting device or an electronic apparatus using the organic electroluminescent device of the present invention, or may serve as a support only in a manufacturing process of the organic electroluminescent device without remaining in a final product.

However, the structure of the organic electroluminescent device according to the present invention is not limited thereto. The organic electroluminescent device can be selected and combined according to the device parameter requirement and the material characteristics, partial organic layers can be added or omitted, and the organic layers with the same function can be made into a laminated structure with more than two layers. The thickness of each organic layer of the organic electroluminescent device is not particularly limited, and may be any thickness commonly used in the art.

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

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

The organic electroluminescent device can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, indication boards, signal lamps and the like.

The present invention is explained more fully by the following examples, but is not intended to be limited thereby. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue burden.

The invention provides a preparation method of a structure shown in a formula I, a formula II and a formula III, but the preparation method is not limited to the above, and the specific synthetic route is as follows:

the synthetic route of formula I:

a synthetic route of formula II:

a synthetic route of formula III:

wherein Xa are the same or different from each other and are selected from any one of Cl, br and I; ar (Ar) ₁ ～Ar ₆ 、Ar _a ～Ar _d 、L、L ₀ 、L ₁ ～L ₆ 、L _a ～L _d 、x、R ₁ 、R ₂ 、n ₁ 、n ₂ The definition of (2) is the same as described above.

The present invention may bond the above substituents by a method known in the art, and the kind and position of substituents or the number of substituents may be changed according to a technique known in the art.

Description of the starting materials, reagents and characterization equipment:

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

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

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

synthesis example 1: preparation of Compound HT-14

Toluene (150 mL), a-HT-14 (40.00 mmol,15.93 g), b-HT-14 (40.00 mmol,6.99 g), palladium acetate (0.60 mmol,0.13 g), sodium t-butoxide (80.00 mmol,7.69 g) and 0.5M P (t-Bu) were added sequentially to the flask under nitrogen ₃ Toluene solution (2.4 ml) was dissolved by stirring and reacted under reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, and toluene/methanol=10: 1 was recrystallized and purified to give HT-14 (15.90 g, yield 81%) with 99.57% purity as determined by HPLC. Mass spectrometrym/z:490.2359 (theory: 490.2347).

Toluene (200 mL), H-316 (30.00 mmol,14.72 g), c-316 (30.00 mmol,8.16 g), pd were added sequentially to the flask under nitrogen ₂ (dba) ₃ (0.30 mmol,0.27 g), sodium t-butoxide (60.00 mmol,5.77 g) and 0.5M P (t-Bu) ₃ Toluene solution (1.2 ml) was dissolved by stirring and reacted under reflux for 6 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, water was then added, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the mixture was recrystallized from toluene to obtain compound 316 (15.52 g, yield 81%) having a purity of 99.94% as measured by HPLC. Mass spectrum m/z:638.2731 (theory: 638.2722). Theoretical element content (%) C ₄₈ H ₃₄ N ₂ : c,90.25; h,5.36; n,4.39. Measured element content (%): c,90.22; h,5.38; n,4.40.

Synthesis example 2: preparation of Compound HT-333

According to the same manner as in Synthesis example 1 except that a-HT-14 was replaced with equimolar a-HT-333 and c-HT-14 was replaced with equimolar c-HT-333, compound HT-333 (13.50 g) was obtained, and the purity of the solid as determined by HPLC was not less than 99.96%. Mass spectrum m/z:576.2549 (theory: 576.2565). Theoretical element content (%) C ₄₃ H ₃₂ N ₂ : c,89.55; h,5.59; n,4.86. Measured element content (%): c,89.53; h,5.60; n,4.87.

Synthesis example 3: preparation of Compound HT-445

According to the same manner as that of Synthesis example 1, alpha-HT-14 was replaced with equimolar alpha-HT-445 and c-HT-14 with equimolar c-HT-445 to obtain Compound HT-445 (16.47 g), and the purity of the solid was not less than 99.93% by HPLC. Mass spectrum m/z:694.3359 (theory: 694.3348). Management deviceTheoretical element content (%) C ₅₂ H ₄₂ N ₂ : c,89.88; h,6.09; n,4.03. Measured element content (%): c,89.91; h,6.08; n,4.01.

Synthesis example 4: preparation of Compound HT-497

According to the same manner as in Synthesis example 1, a-HT-14 was replaced with equimolar a-HT-497 and c-HT-14 with equimolar c-HT-497, to obtain compound HT-497 (17.06 g), and the purity of the solid as measured by HPLC was not less than 99.92%. Mass spectrum m/z:710.3130 (theory: 710.3117). Theoretical element content (%) C ₅₁ H ₄₂ N ₂ Si: c,86.16; h,5.95; n,3.94. Measured element content (%): c,86.20; h,5.93; n,3.92.

Synthesis example 5: preparation of Compound HT-772

M-HT-772 (24.59 g,90 mmol), n-HT-772 (15.23 g,90 mmol), sodium t-butoxide (15.38 g,160 mmol) were added to 400mL toluene under nitrogen, palladium acetate (0.22 g,1.00 mmol), tri-t-butylphosphine (4.0 mL of 0.50M toluene solution, 2.00 mmol) were added with stirring, and the mixture of the above reactants was heated to reflux for 3.5h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, suction-filtering, and recrystallizing the obtained solid with ethyl acetate to obtain an intermediate M-HT-772 (26.03 g, 80%), wherein the HPLC purity is not less than 99.81%. Mass spectrum m/z:361.1815 (theory: 361.1830).

M-HT-772 (19.88 g,55 mmol), g-HT-772 (14.72 g,55 mmol) and sodium tert-butoxide (11.53 g,120 mmol) were added to 400ml toluene under nitrogen and Pd (OAc) was added under stirring ₂ (0.13g，0.60mmol)、P(t-Bu) ₃ (2.4 mL of 0.5M)Toluene solution, 1.20 mmol) and the mixture of the above reactants were heated to reflux for 4.0h. After the reaction was completed, cooling to room temperature, adding distilled water, extracting with methylene chloride, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by distillation under reduced pressure, cooling for crystallization, suction-filtering, and recrystallizing the obtained solid with toluene/ethanol=8/1 to obtain an intermediate Q-HT-772 (22.91 g, 76%), wherein the HPLC purity is not less than 99.87%. Mass spectrum m/z:547.2079 (theory: 547.2067).

Q-HT-772 (16.44 g,30 mmol), N-HT-772 (9.64 g,30 mmol), sodium tert-butoxide (7.21 g,75 mmol) were added to 200ml toluene under nitrogen and Pd was added under stirring ₂ (dba) ₃ (0.27g，0.30mmol)、P(t-Bu) ₃ (1.2 mL of a 0.5M toluene solution, 0.60 mmol) and the mixture of the above reactants was heated under reflux for 6.0h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by distillation under reduced pressure, cooling for crystallization, suction-filtering, and recrystallizing the obtained solid with toluene to obtain a compound HT-772 (18.49 g, yield 74%), wherein the HPLC purity is not less than 99.95%. Mass spectrum m/z:832.3830 (theory: 832.3817). Theoretical element content (%) C ₆₃ H ₄₈ N ₂ : c,90.83; h,5.81; n,3.36. Measured element content (%): c,90.82; h,5.79; n,3.37.

Synthesis example 6: preparation of Compound HT-850

Under the protection of nitrogen, g-HT-850 (9.36 g,30.00 mmol), M-HT-850 (19.89 g,66.00 mmol) and Pd ₂ (dba) ₃ (0.55 g,0.60 mmol), sodium t-butoxide (8.65, 90.00 mmol) and BINAP (0.75 g,1.20 mmol) were added to 400ml toluene and the mixture of the above reactants was heated under reflux for 5.0h. After completion of the reaction, cooled to room temperature, water was added, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and recrystallized from toluene to give compound HT-850 (17.85 g, yield 79) % of HPLC purity ≡ 99.96%. Mass spectrum m/z:752.4143 (theory: 752.4130). Theoretical element content (%) C ₅₆ H ₅₂ N ₂ : c,89.32; h,6.96; n,3.72. Measured element content (%): c,89.36; h,6.95; n,3.69.

Synthesis example 7: preparation of intermediate B-2-251

Step 1: 100mL of anhydrous tetrahydrofuran solvent was added to magnesium turnings (5.08 g,420 mmol) under nitrogen protection, then three pieces of iodine were added, a tetrahydrofuran solution (200 mL) of b-2-251 (91.68 g,400 mmol) was slowly added dropwise, the reaction was initiated in a format, after the dropwise addition was completed, the reaction was carried out at room temperature for 7 hours, and after the completion of the reaction, the mixture was cooled to room temperature.

Step 2: under the protection of nitrogen, a-2-251 (73.76 g,400 mmol) is added into a reaction bottle, then 400mL of tetrahydrofuran solvent is added, the system temperature is reduced to minus 5 ℃, then the format reagent prepared in the step 1 is slowly dripped for 2-3 hours, the reaction is carried out for 6 hours at minus 5 ℃ after the dripping is finished, after the reaction is finished, the reaction solution is poured into 12% dilute hydrochloric acid, after the reaction is fully stirred for 30 minutes, dichloromethane is used for extraction (300 mL multiplied by 3 times), the organic phase is separated, the organic phase is dried by anhydrous magnesium sulfate, the solvent is concentrated by vacuum distillation, and the solvent is recrystallized by tetrahydrofuran after suction filtration, thus obtaining an intermediate A-2-251 (85.89 g, yield 72%) with HPLC purity of not less than 99.81 percent. Mass spectrum m/z:297.0226 (theory: 297.0256).

Step 3: to the reaction flask was added intermediate A-2-251 (59.65 g,200 mmol), c-2-251 (50.82 g,200 mmol), anhydrous potassium carbonate (52.52 g,380 mmol), then 500mL of toluene solution, 3 times replaced with nitrogen, and tetrakis (triphenylphosphine) palladium (2.31 g,2.0 mmol) was added thereto under nitrogen atmosphere, followed by stirring and heating for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the solvent was concentrated by distillation under reduced pressure, the filter cake was then washed with ethanol, and the obtained filter cake was recrystallized from toluene to give intermediate B-2-251 (64.20 g, yield 68%), which had an HPLC purity of 99.77%. Mass spectrum m/z:471.0963 (theory: 471.0992).

Synthesis example 8: preparation of intermediate B-2-276

According to the same manner as that of intermediate B-2-251 in Synthesis example 7, c-2-251 was replaced with equimolar c-2-276, and the other steps were the same, to obtain intermediate B-2-251 (50.91 g), and the purity of the solid was not less than 99.80% as measured by HPLC. Mass spectrum m/z:379.0912 (theory: 379.0908).

Synthesis example 9: preparation of intermediate B-2-393

According to the same manner as in Synthesis example 7, intermediate B-2-251 was obtained by substituting c-2-251 with equimolar c-2-293 and by carrying out the same steps, intermediate B-2-293 (58.61 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.84%. Mass spectrum m/z:395.1555 (theory: 395.1585).

Synthesis example 10: preparation of intermediate B-2-578

According to the same manner as in Synthesis example 7, intermediate B-2-251 was obtained by substituting c-2-251 with equimolar c-2-578 and by carrying out the other steps in the same manner, intermediate B-2-578 (58.94 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.81%. Mass spectrum m/z:420.1570 (theory: 420.1585).

Synthesis example 11: preparation of intermediate B-2-578

According to the same manner as in Synthesis example 7, intermediate B-2-251 was obtained by substituting c-2-251 with equimolar c-2-579 and by carrying out the other steps in the same manner, intermediate B-2-579 (52.39 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.79%. Mass spectrum m/z:390.1080 (theory: 390.1068).

Synthesis example 12: preparation of Compound 2-1

Preparation of F-2-1:

d-2-1 (74.06 g,240 mmol), E-2-1 (73.27 g,240 mmol) and potassium carbonate (62.19 g,450 mmol) were added to a reaction flask under nitrogen protection, then 750mL of toluene/ethanol/water mixed solvent (vtoluene: vethanol: vwater=2:1:1) was added, then tetrakis (triphenylphosphine) palladium (2.77 g,2.4 mmol) was added to the flask and reacted for 3 hours under stirring and refluxing conditions, after the reaction was completed, the reaction was cooled to room temperature, distilled water was added, the mixture was left to stand for liquid separation, the separated organic phase was concentrated by distillation under reduced pressure, the solvent was suction filtered, the filter cake was washed with ethanol, and the obtained filter cake was recrystallized with toluene/ethanol (vtoluene: vethanol=10:1) to give F-2-1 (85.70 g, 73%), HPLC purity ∈ 99.78%, mass spectrum m/z:488.1761 (theory: 488.1727).

Preparation of G-2-1:

f-2-1 (73.37 g,150 mmol), pinacol diboronate (40.63 g,160 mmol), KOAc (39.26 g,400 mmol) and then 500mL of 1, 4-dioxane were added under nitrogen, after 3 changes of air, pd (dppf) Cl was added ₂ (1.10G, 1.5 mmol) under heating, stirring and reacting for 7.5 hours, after the reaction, cooling the reaction to room temperature, adding distilled water, extracting with dichloromethane (700 mL. Times.3), separating the organic phase, drying the organic phase with anhydrous magnesium sulfate, and recrystallizing the obtained solid with toluene to obtain G-2-1 (70.55G, 81%), HPLC purity > 99.89%, mass spectrum m/z:580.2902 (theory: 580.2969).

Preparation of Compound 2-1:

g-2-1 (58.06G, 100 mmol), B-2-1 (26.67G, 100 mmol), potassium carbonate (27.64G,200 mmol) and then 450mL of toluene/ethanol/water mixture (v toluene: v ethanol: vwater=2:1:1), then Pd2 (dba) was added ₃ (0.92 g,1.0 mmol), (4.0 mL,2.0 mmol) P (t-Bu) ₃ (0.5M toluene solution), heating and stirring for 8 hours, cooling the reactant to room temperature after the reaction is finished, adding distilled water, standing and separating liquid, concentrating the solvent by reduced pressure distillation of the separated organic phase, suction-filtering, flushing the filter cake with ethanol and distilled water, and recrystallizing the obtained filter cake with toluene to obtain the compound 2-1 (47.26 g, 69%), wherein the HPLC purity is equal to or higher than 99.95%, and the mass spectrum M/z:684.2956 (theory: 684.2961). Theoretical element content (%) C ₄₉ H ₄₀ N ₂ Si: c,85.92; h,5.89; n,4.09. Measured element content (%): c,85.91; h,5.89; n,4.10.

Synthesis example 13: preparation of Compounds 2-17

According to the same production method as that of Compound 2-1 in Synthesis example 12, F-2-1 and B-2-1 were replaced with equimolar F-2-17 and B-2-17, respectively, and the other steps were the same, to obtain Compound 2-17 (46.07 g), and the purity of the solid was not less than 99.93% as measured by HPLC. Mass spectrum m/z:648.2956 (theory: 648.2961). Theoretical element content (%) C ₄₆ H ₄₀ N ₂ Si: c,85.14; h,6.21; n,4.32. Measured element content (%): c,85.10; h,6.28; n,4.35.

Synthesis example 14: preparation of Compounds 2-28

According to the same production method as that of Compound 2-1 in Synthesis example 12, B-2-1 was replaced with equimolar B-2-28, and the other steps were the same, to give Compound 2-28 (50.76 g), and the purity of the solid was not less than 99.95% as measured by HPLC. Mass spectrum m/z:685.2984 (theory: 685.2913). Theoretical element content (%) C ₄₈ H ₃₉ N ₃ Si：C,85.05；H,5.73；N,6.13. Measured element content (%): c,85.01; h,5.71; n,6.20.

Synthesis example 15: preparation of Compounds 2-42

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, F-2-17 and B-2-42, respectively, and the other steps were the same, to obtain Compound 2-42 (54.67 g), and the purity of the solid was not less than 99.91% as measured by HPLC. Mass spectrum m/z:780.3362 (theory: 780.3333). Theoretical element content (%) C ₄₈ H ₃₉ N ₃ Si: c,83.04; h,5.94; n,5.38. Measured element content (%): c,83.08; h,5.92; n,5.36.

Synthesis example 16: preparation of Compounds 2-46

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, E-2-46 and B-2-46, respectively, and the other steps were the same, to give Compound 2-46 (56.86 g), and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:757.3371 (theory: 757.3309). Theoretical element content (%) C ₅₁ H ₄₇ N ₃ Si ₂ : c,80.80; h,6.25; n,5.54. Measured element content (%): c,80.78; h,5.24; n,5.56.

Synthesis example 17: preparation of Compounds 2-65

According to the same manner as in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, E-2-65 and B-2-28, respectively, and the other steps were the same, to give Compound 2-65 (41.63 g), which was examined by HPLCThe bulk purity is more than or equal to 99.98 percent. Mass spectrum m/z:533.2256 (theory: 533.2287). Theoretical element content (%) C ₃₆ H ₃₁ N ₃ Si: c,81.01; h,5.85; n,7.87. Measured element content (%): c,81.02; h,5.86; n,7.86.

Synthesis example 18: preparation of Compounds 2-67

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-67, E-2-67 and B-2-67, respectively, and the other steps were the same, to obtain Compound 2-67 (50.23 g), and the purity of the solid as measured by HPLC was not less than 99.94%. Mass spectrum m/z:727.3378 (theory: 727.3383). Theoretical element content (%) C ₅₁ H ₄₅ N ₃ Si: c,84.14; h,6.23; n,5.77. Measured element content (%): c,84.11; h,6.28; n,5.79.

Synthesis example 19: preparation of Compounds 2-118

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, E-2-118 and B-2-118, respectively, and the other steps were the same, to obtain Compound 2-118 (39.59 g), and the purity of the solid was not less than 99.91% as measured by HPLC. Mass spectrum m/z:590.2852 (theory: 590.2883). Theoretical element content (%) C ₄₀ H ₂₆ D ₇ N ₃ Si: c,81.31; h,6.82; n,7.11. Measured element content (%): c,81.31; h,6.83; n,7.10.

Synthesis example 20: preparation of Compounds 2-119

According to the phase with Compound 2-1 in Synthesis example 12The same preparation method respectively replaces D-2-1, E-2-1 and B-2-1 with equimolar D-2-42, E-2-65 and B-2-119, and other steps are the same, thus obtaining the compound 2-119 (46.07 g), wherein the purity of the solid detected by HPLC is more than or equal to 99.93%. Mass spectrum m/z:639.2133 (theory: 639.2164). Theoretical element content (%) C ₄₂ H ₃₃ N ₃ SSi: c,78.84; h,5.20; n,6.57. Measured element content (%): c,78.85; h,5.19; n,6.57.

Synthesis example 21: preparation of Compounds 2-126

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-126, E-2-126 and B-2-126, respectively, and the other steps were the same, to obtain Compound 2-126 (36.23 g), and the purity of the solid as measured by HPLC was not less than 99.91%. Mass spectrum m/z:532.2304 (theory: 532.2335). Theoretical element content (%) C ₃₇ H ₃₂ N ₂ Si: c,83.42; h,6.05; n,5.26. Measured element content (%): c,83.40; h,6.09; n,5.25.

Synthesis example 22: preparation of Compounds 2-159

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-159, E-2-126 and B-2-28, respectively, and the other steps were the same, to give Compound 2-159 (45.13 g), and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:609.2669 (theory: 609.2600). Theoretical element content (%) C ₄₂ H ₃₅ N ₃ Si: c,82.72; h,5.79; n,6.89. Measured element content (%): c,82.77; h,5.77; n,6.94.

Synthesis example 23: preparation of Compounds 2-217

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-217, E-2-217 and B-2-217, respectively, and the other steps were the same, to obtain Compound 2-217 (47.94 g), and the purity of the solid as measured by HPLC was not less than 99.90%. Mass spectrum m/z:704.2987 (theory: 704.2909). Theoretical element content (%) C ₄₇ H ₃₂ D ₄ N ₄ OSi: c,80.08; h,5.72; n,7.95. Measured element content (%): c,80.08; h,5.71; n,7.95.

Synthesis example 24: preparation of Compounds 2-241

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1 and B-2-1 were replaced with equimolar D-2-42 and B-2-241, respectively, and the other steps were the same, to obtain Compound 2-241 (51.12 g), and the purity of the solid was not less than 99.93% as measured by HPLC. Mass spectrum m/z:709.2942 (theory: 709.2913). Theoretical element content (%) C ₅₀ H ₃₉ N ₃ Si: c,84.59; h,5.54; n,5.92. Measured element content (%): c,84.60; h,5.53; n,5.92.

Synthesis example 25: preparation of Compounds 2-251

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-251, E-2-251 and B-2-251, respectively, and the other steps were the same, to obtain Compound 2-251 (52.01 g), and the purity of the solid as measured by HPLC was not less than 99.92%. Mass spectrum m/z:742.2557 (theory: 742.2586). Theoretical element content (%) C ₄₉ H ₃₈ N ₄ SSi: c,79.21; h,5.16; n,7.54. Measured element content (%): c,79.26; h,5.10; n,7.53.

Synthesis example 26: preparation of Compounds 2-269

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-269, E-2-269 and B-2-28, respectively, and the other steps were the same, to obtain Compound 2-269 (43.74 g), and the purity of the solid as measured by HPLC was not less than 99.93%. Mass spectrum m/z:633.2621 (theory: 633.2600). Theoretical element content (%) C ₄₄ H ₃₅ N ₃ Si: c,83.37; h,5.57; n,6.63. Measured element content (%): c,83.34; h,5.58; n,6.65.

Synthesis example 27: preparation of Compounds 2-276

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-276, E-2-276 and B-2-276, respectively, and the other steps were the same, to obtain Compound 2-276 (48.51 g), and the purity of the solid as measured by HPLC was not less than 99.90%. Mass spectrum m/z:723.2734 (theory: 723.2706). Theoretical element content (%) C ₅₀ H ₃₇ N ₃ OSi: c,82.95; h,5.15; n,5.80. Measured element content (%): c,82.91; h,5.19; n,5.81.

Synthesis example 28: preparation of Compounds 2-279

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-279, E-2-279 and B-2-279, respectively, and the other steps were the same, to obtain Compound 2-279 (48.09 g), and the purity of the solid was not less than 99.95% as measured by HPLC. Mass spectrum m/z:649.2942 (theory: 649.2913). Theoretical element content(％)C ₄₅ H ₃₉ N ₃ Si: c,83.16; h,6.05; n,6.47. Measured element content (%): c,83.19; h,6.03; n,6.46.

Synthesis example 29: preparation of Compounds 2-287

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-279, E-2-287 and B-2-287, respectively, and the other steps were the same, to obtain Compound 2-287 (62.06 g), and the purity of the solid as measured by HPLC was not less than 99.94%. Mass spectrum m/z:849.3540 (theory: 849.3539). Theoretical element content (%) C ₆₁ H ₄₇ N ₃ Si: c,86.18; h,5.57; n,4.94. Measured element content (%): c,86.14; h,5.59; n,4.96.

Synthesis example 30: preparation of Compound 2-289

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-279, E-2-289 and B-2-28, respectively, and the other steps were the same, to give Compound 2-289 (48.86 g), and the purity of the solid was not less than 99.91% by HPLC detection. Mass spectrum m/z:697.2926 (theory: 697.2913). Theoretical element content (%) C ₄₉ H ₃₉ N ₃ Si: c,84.32; h,5.63; n,6.02. Measured element content (%): c,84.30; h,5.64; n,6.03.

Synthesis example 31: preparation of Compounds 2-330

According to the same manner as in preparation of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1, B-2-1 were replaced with equimolar amounts of D-2-42, E-2-330, B-2, respectively-28, the other steps being identical, obtaining compound 2-330 (60.78 g), the purity of the solid being greater than or equal to 99.97% by HPLC detection. Mass spectrum m/z:843.3436 (theory: 843.3465). Theoretical element content (%) C ₅₈ H ₄₉ N ₃ Si ₂ : c,82.52; h,5.85; n,4.98. Measured element content (%): c,82.55; h,5.82n,4.97.

Synthesis example 32: preparation of Compounds 2-342

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-279, E-2-342 and B-2-342, respectively, and the other steps were the same, to obtain Compound 2-342 (45.33 g), and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:573.2659 (theory: 573.2600). Theoretical element content (%) C ₃₉ H ₃₅ N ₃ Si: c,81.63; h,6.15; n,7.32. Measured element content (%): c,81.63; h,6.12; n,7.34.

Synthesis example 33: preparation of Compounds 2-393

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, E-2-393 and B-2-393, respectively, and the other steps were the same, to give Compound 2-393 (51.54 g), and the purity of the solid was not less than 99.92% by HPLC detection. Mass spectrum m/z:705.3548 (theory: 705.3539). Theoretical element content (%) C ₄₉ H ₄₇ N ₃ Si: c,83.36; h,6.71; n,5.95. Measured element content (%): c,83.38h,6.72; n,5.93.

Synthesis example 34: preparation of Compounds 2-401

According to the same production method as that of Compound 2-1 in Synthesis example 12, F-2-1 and B-2-1 were replaced with equimolar F-2-401 and B-2-46, respectively, and the other steps were the same, to obtain Compound 2-401 (55.45 g), and the purity of the solid was not less than 99.96% as measured by HPLC. Mass spectrum m/z:769.3320 (theory: 769.3309). Theoretical element content (%) C ₅₂ H ₄₇ N ₃ Si ₂ : c,81.10; h,6.15; n,5.46. Measured element content (%): c,81.09; h,6.12; n,5.48.

Synthesis example 35: preparation of Compounds 2-442

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-279, E-2-442 and B-2-442, respectively, and the other steps were the same, to obtain Compound 2-442 (52.92 g), and the purity of the solid was not less than 99.90% as measured by HPLC. Mass spectrum m/z:813.4290 (theory: 813.4275). Theoretical element content (%) C ₅₆ H ₄₇ D ₅ N ₄ Si: c,82.61; h,7.06; n,6.88. Measured element content (%): c,82.59; h,7.08; n,6.90.

Synthesis example 36: preparation of Compounds 2-453

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-279, E-2-342 and B-2-453, respectively, and the other steps were the same, to obtain Compound 2-453 (59.07 g), and the purity of the solid as measured by HPLC was not less than 99.94%. Mass spectrum m/z:797.3654 (theory: 797.3622). Theoretical element content (%) C ₅₄ H ₅₁ N ₃ Si ₂ : c,81.26; h,6.44; n,5.26. Measured element content (%): c,81.23; h,6.43; n,5.29.

Synthesis example 37: preparation of Compound 2-488

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-488, E-2-342 and B-2-342, respectively, and the other steps were the same, to give Compound 2-488 (50.37 g), and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:689.3275 (theory: 689.3226). Theoretical element content (%) C48H43N3Si: c,83.56; h,6.28; n,6.09. Measured element content (%): c,83.55; h,6.24; n,6.13.

Synthesis example 38: preparation of Compounds 2-529

According to the same production method as that of the compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-529, E-2-529 and B-2-342, respectively, and the other steps were the same, to obtain the compound 2-529 (46.79 g), and the purity of the solid as measured by HPLC was not less than 99.94%. Mass spectrum m/z:649.2930 (theory: 649.2913). Theoretical element content (%) C ₄₅ H ₃₉ N ₃ Si: c,83.16; h,6.05; n,6.47. Measured element content (%): c,83.17; h,6.09; n,6.50.

Synthesis example 39: preparation of Compounds 2-556

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, E-2-556 and B-2-342, respectively, and the other steps were the same, to obtain Compound 2-556 (48.10 g), and the purity of the solid as measured by HPLC was not less than 99.90%. Mass spectrum m/z:739.3008 (theory: 739.3019). Theoretical element content (%) C ₅₁ H ₄₁ N ₃ OSi: c,82.78; h,5.58; n,5.68. Measured element content (%): c,82.80；H,5.61；N,5.65。

Synthesis example 40: preparation of Compounds 2-576

According to the same manner as in Synthesis example 12, E-2-1 and B-2-1 were replaced with equimolar E-2-65 and B-2-46, respectively, and the other steps were the same, to give Compound 2-576 (55.81 g), and the purity of the solid was not less than 99.96% as measured by HPLC. Mass spectrum m/z:753.3378 (theory: 753.3391). Theoretical element content (%) C ₄₈ H ₅₁ N ₃ Si ₃ : c,76.44; h,6.82; n,5.57. Measured element content (%): c,76.45; h,6.79; n,5.60.

Synthesis example 41: preparation of Compounds 2-578

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, E-2-578 and B-2-578, respectively, and the other steps were the same, to obtain Compound 2-578 (48.64 g), and the purity of the solid was not less than 99.92% as measured by HPLC. Mass spectrum m/z:704.3037 (theory: 704.3020). Theoretical element content (%) C ₄₈ H ₃₂ D ₅ N ₃ OSi: c,81.78; h,6.00; n,5.96. Measured element content (%): c,81.80; h,6.04; n,5.95.

Synthesis example 42: preparation of Compounds 2-579

According to the same manner as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-579, E-2-579 and B-2-579, respectively, and the other steps were the same, to give Compound 2-579 (48.64 g), and the purity of the solid as measured by HPLC was not less than 99.93%. Mass spectrum m And/z: 674.2516 (theory: 674.2502). Theoretical element content (%) C ₄₅ H ₃₄ N ₄ OSi: c,80.09; h,5.08; n,8.30. Measured element content (%): c,80.11; h,5.10; n,8.28.

Synthesis example 43: preparation of Compounds 2-580

According to the same production method as that of Compound 2-1 in Synthesis example 12, D-2-1, E-2-1 and B-2-1 were replaced with equimolar amounts of D-2-42, E-2-580 and B-2-580, respectively, and the other steps were the same, to give Compound 2-580 (53.20 g), and the purity of the solid as measured by HPLC was not less than 99.91%. Mass spectrum m/z:759.3052 (theory: 759.3070). Theoretical element content (%) C ₅₄ H ₄₁ N ₃ Si: c,85.34; h,5.44; n,5.53. Measured element content (%): c,85.36; h,5.41; n,5.50.

Device example 1

Firstly, the ITO substrate is placed in distilled water for ultrasonic cleaning for 3 times, ultrasonic cleaning is carried out for 15 minutes each time, after the distilled water cleaning is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially used for ultrasonic cleaning, ultrasonic cleaning is carried out for 10 minutes each time, and after the cleaning is finished, drying is carried out at 120 ℃.

Evaporating HI-1 with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating a compound HT-1 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; evaporating RH, RD-1=97:3 (mass ratio) serving as a light-emitting layer on the hole transport layer, wherein the evaporating thickness is 40nm; evaporating compounds 2-159 on the light-emitting layer as electron transport layer material, wherein the evaporating thickness is 25nm; evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1.0nm; and then evaporating Al on the electron injection layer to serve as a cathode, wherein the evaporating thickness is 120nm, so that the organic electroluminescent device is prepared.

Device examples 2 to 15

The same procedure as in device example 1 was used to prepare an organic electroluminescent device by substituting compound HT-14 and compound 2-330, compound HT-22 and compound 2-287, compound HT-94 and compound 2-42, compound HT-113 and compound 2-67, compound HT-140 and compound 2-576, compound HT-201 and compound 2-28, compound HT-333 and compound 2-580, compound HT-369 and compound 2-453, compound HT-389 and compound 2-17, compound HT-445 and compound 2-119, compound HT-471 and compound 2-126, compound HT-497 and compound 2-393, compound HT-511 and compound 2-241, and compound HT-516 and compound 2-529 for compound HT-1 and compound 2-159 in device example 1.

Comparative device examples 1 to 8

An organic electroluminescent device was prepared by using the same procedure as in device example 1, except that compound HT-14 and comparative compound 1, compound HT-511 and comparative compound 1, compound HT-22 and comparative compound 2, compound HT-113 and comparative compound 2, compound HT-445 and comparative compound 3, compound HT-333 and comparative compound 3, compound HT-389 and comparative compound 4, and compound HT-94 and comparative compound 4 were used in place of compound HT-1 and compound 2-159 in device example 1.

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

The results of testing the light emitting characteristics of the devices 1 to 15 in the device examples according to the present invention and the organic electroluminescent devices obtained in the comparative examples 1 to 8 are shown in table 1 below.

Device example 16

Evaporating HI-2 with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating a compound HT-1 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; evaporating GH:GD-1=92:8 (mass ratio) on the hole transport layer as a light-emitting layer, wherein the evaporating thickness is 40nm; evaporating compounds 2-65 on the light-emitting layer to serve as a hole blocking layer material, wherein the evaporating thickness is 30nm; evaporating ET-1 on the hole blocking layer as an electron transport layer material, wherein the evaporating thickness is 28nm; evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1.0nm; and then evaporating Al on the electron injection layer to serve as a cathode, wherein the evaporating thickness is 120nm, so that the organic electroluminescent device is prepared.

Device examples 17 to 30

The same procedure as in device example 16 was used to prepare an organic electroluminescent device by substituting compound HT-14 and compound 2-289, compound HT-22 and compound 2-279, compound HT-94 and compound 2-269, compound HT-113 and compound 2-118, compound HT-140 and compound 2-576, compound HT-201 and compound 2-342, compound HT-333 and compound 2-276, compound HT-369 and compound 2-46, compound HT-389 and compound 2-1, compound HT-445 and compound 2-556, compound HT-471 and compound 2-579, compound HT-497 and compound 2-578, compound HT-511 and compound 2-217, and compound HT-516 and compound 2-488 for compound HT-1 and compound 2-65 in device example 1.

Comparative device examples 9 to 12

An organic electroluminescent device was fabricated by using the same procedure as in device example 16, except that compound HT-140 and comparative compound 1, compound HT-369 and comparative compound 2, compound HT-516 and comparative compound 3, and compound HT-14 and comparative compound 4 were used in place of compound HT-1 and compound 2-65 in device example 1.

Comparative device example 13

Evaporating HI-2 with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating a compound HT-497 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; evaporating GH:GD-1=92:8 (mass ratio) on the hole transport layer as a light-emitting layer, wherein the evaporating thickness is 40nm; evaporating ET-1 on the light-emitting layer as an electron transport layer material, wherein the evaporating thickness is 58nm; evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1.0nm; and then evaporating Al on the electron injection layer to serve as a cathode, wherein the evaporating thickness is 120nm, so that the organic electroluminescent device is prepared.

Comparative device examples 14 to 16

An organic electroluminescent device was fabricated by using the same procedure as in comparative device example 13, except that compound HT-1, compound HT-511, and compound HT-113 were used in place of compound HT-497 in comparative device example 13.

The results of the light emitting characteristics of the devices 16 to 30 in the device examples of the present invention and the organic electroluminescent devices obtained in the comparative examples 9 to 16 were as follows

Table 2 shows the results.

Device example 31

Evaporating HI-1 with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating a compound HT-522 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; evaporating RH, RD-2=98:2 (mass ratio) on the hole transport layer to serve as a light-emitting layer, wherein the evaporating thickness is 40nm; evaporating compound 2-401 as electron transport layer material on the light emitting layer, wherein the evaporating thickness is 28nm; evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 0.8nm; and then evaporating Al on the electron injection layer to serve as a cathode, wherein the evaporating thickness is 120nm, so that the organic electroluminescent device is prepared.

Device examples 32 to 48

Substituting compound HT-528 and compound 2-393, compound HT-537 and compound 2-529, compound HT-541 and compound 2-1, compound HT-547 and compound 2-251, compound HT-625 and compound 2-118, compound HT-654 and compound 2-159, compound HT-666 and compound 2-576, compound HT-692 and compound 2-46, compound HT-701 and compound 2-269, compound HT-715 and compound 2-580, compound HT-743 and compound 2-579, compound HT-772 and compound 2-330, compound HT-783 and compound 2-442, compound HT-801 and compound 2-67, compound HT-848 and compound 2-126, compound HT-850 and compound 2-276, compound HT-851 and compound 2-42 for compound HT-522 and compound 2-401 in device example 31, except for this, an organic electroluminescent device was produced by applying the same procedure as in device example 31.

Comparative device examples 17 to 24

An organic electroluminescent device was fabricated by using the same procedure as in device example 31, except that compound HT-541 and comparative compound 1, compound HT-715 and comparative compound 1, compound HT-801 and comparative compound 2, compound HT-625 and comparative compound 2, compound HT-851 and comparative compound 3, compound HT-850 and comparative compound 3, compound HT-848 and comparative compound 4, and compound HT-743 and comparative compound 4 were used instead of compound HT-522 and compound 2-401 in device example 31.

The results of testing the light emitting characteristics of the devices 31 to 48 in the device examples according to the present invention, and the organic electroluminescent devices obtained in comparative examples 17 to 24 are shown in table 3 below.

Device example 49

Evaporating HI-2 with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating a compound HT-522 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; evaporating GH:GD-2=93:7 (mass ratio) on the hole transport layer as a light-emitting layer, wherein the evaporating thickness is 40nm; evaporating compounds 2-453 on the light-emitting layer to serve as a hole blocking layer material, wherein the evaporating thickness is 40nm; evaporating ET-2 on the hole blocking layer as an electron transport layer material, wherein the evaporating thickness is 28nm; evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 0.8nm; and then evaporating Al on the electron injection layer to serve as a cathode, wherein the evaporating thickness is 120nm, so that the organic electroluminescent device is prepared.

Device examples 50 to 66

The same procedure for the preparation of an organic electroluminescent device was carried out as in example 49, except that compound HT-528 and compound 2-28, compound HT-537 and compound 2-342, compound HT-541 and compound 2-287, compound HT-547 and compound 2-279, compound HT-625 and compound 2-556 and compound 2-529, compound HT-666 and compound 2-576, compound HT-692 and compound 2-46, compound HT-701 and compound 2-42, compound HT-715 and compound 2-241, compound HT-743 and compound 2-126, compound HT-772 and compound 2-65, compound HT-783 and compound 2-289, compound HT-801 and compound 2-251, compound HT-848 and compound 2-276, compound HT-850 and compound 2-580, and compound HT-851 and compound 2-1 were used instead of compound HT-522 and compound 2-453 in example 49.

Comparative device examples 25 to 28

An organic electroluminescent device was manufactured by using the same procedure as in device example 49, except that compound HT-528 and comparative compound 1, compound HT-537 and comparative compound 2, compound HT-772 and comparative compound 3, and compound HT-547 and comparative compound 4 were used instead of compound HT-522 and compound 2-453 in device example 49.

Comparative device example 29

Evaporating HI-2 with the thickness of 10nm on the cleaned ITO substrate by adopting a vacuum evaporation method to serve as a hole injection layer material; evaporating a compound HT-783 with the thickness of 80nm on the hole injection layer to serve as a hole transport layer material; evaporating GH:GD-2=93:7 (mass ratio) on the hole transport layer as a light-emitting layer, wherein the evaporating thickness is 40nm; evaporating ET-2 on the light-emitting layer as an electron transport layer material, wherein the evaporating thickness is 68nm; evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 0.8nm; and then evaporating Al on the electron injection layer to serve as a cathode, wherein the evaporating thickness is 120nm, so that the organic electroluminescent device is prepared.

Comparative device examples 30 to 32

An organic electroluminescent device was fabricated by using the same procedure as in comparative device example 29, except that compound HT-541, compound HT-715, and compound HT-625 were used in place of compound HT-783 in comparative device example 29.

The results of testing the light emitting characteristics of the devices 49 to 66 in the device examples according to the present invention and the organic electroluminescent devices obtained in the comparative examples 25 to 32 are shown in the following table 4.

As can be seen from the data results in tables 1 to 4, the hole transport layer material of the compound of formula I or formula II according to the present invention as a hole transport region is matched with the hole blocking layer material or electron transport layer material of the compound of formula III according to the present invention as an electron transport region, and the light emitting efficiency and the service life of the device are significantly improved as compared with the comparative device examples.

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

Claims

1. An organic electroluminescent device comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a hole transmission region, a luminescent layer, an electron transmission region and a covering layer, and is characterized in that the hole transmission region comprises any one of structures shown in a formula I or a formula II, and the electron transmission region comprises a structure shown in a formula III;

the R is ₁ Are identical or different from each other and are selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstitutedAny one of substituted C2-C30 heteroaryl;

2. An organic electroluminescent device as claimed in claim 1, wherein Ar ₁ 、Ar ₂ Are the same or different from each other, and are selected from any one of the structures shown below;

the R is ₃ Identical to each other orDifferently, any one selected from hydrogen, deuterium, or a group shown below substituted or unsubstituted with one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, triphenylsilyl, ethyldimethylsilyl, t-butyldimethylsilyl, benzocyclopropyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptyl, benzocyclopentenyl, or benzocyclohexenyl;

the a ₁ Selected from 0, 1, 2, 3, 4 or 5, said a ₂ Selected from 0, 1, 2, 3 or 4, said a ₃ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said a ₄ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said a ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said a ₆ Selected from 0, 1, 2 or 3, said a ₇ Selected from 0, 1, 2, 3, 4, 5 or 6, said a ₈ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said a ₉ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, said a ₁₀ Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, said a ₁₁ Selected from 0, 1 or 2.

3. An organic electroluminescent device as claimed in claim 1, wherein Ar ₃ Selected from any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C6 alkyl, silyl groups: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzeneAnd cyclopentenyl, benzocyclohexenyl, benzofuranyl, benzothienyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl or naphthyridinyl.

4. An organic electroluminescent device as claimed in claim 1, wherein Ar _a -Ar _d Are the same or different from each other, and are selected from any one of the structures shown below;

the R is ₅ Are the same or different from each other, and are selected from any one of hydrogen, deuterium, or a group shown as the following which is substituted or unsubstituted by one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, triphenylsilyl, ethyldimethylsilyl, t-butyldimethylsilyl, benzocyclopropenyl A benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, or benzocyclohexenyl group;

said b ₁ Selected from 0, 1, 2, 3, 4 or 5, said b ₂ Selected from 0, 1, 2, 3 or 4, said b ₃ Selected from 0, 1, 2 or 3, said b ₄ Selected from 0, 1, 2, 3, 4, 5, 6 or 7, said b ₅ Selected from 0, 1, 2, 3, 4, 5 or 6, said b ₆ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, when two or more R's are present ₅ When two or more R' s ₅ Identical or different from each other, or adjacent two R ₅ May be linked to each other to form a substituted or unsubstituted ring.

5. An organic electroluminescent device as claimed in claim 1, wherein the L ₀ Selected from any one of the structures shown below;

The c ₁ Selected from 0, 1, 2, 3 or 4, said c ₂ Selected from 0, 1, 2 or 3, said c ₃ Selected from 0, 1 or 2The c ₄ Selected from 0, 1, 2, 3, 4, 5 or 6, said c ₅ Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

6. An organic electroluminescent device as claimed in claim 1, wherein Ar ₄ -Ar ₆ Are the same or different from each other, and are selected from any one of the structures shown below;

the t is ₂ Selected from CH or N atoms;

the R is _x 、R _y Are identical or different from each other and are selected from hydrogen, deuterium, halogen, cyano or alkyl groups which are substituted by one or more deuterium, C1-C6, -Si (R) ₄ ) ₃ A substituted or unsubstituted group of any of the following: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzocyclobutanyl, benzocyclopentyl, benzocyclohexenyl, benzocycloheptyl, benzocyclopentenyl, benzofuranyl or benzothienyl, or R _x 、R _y May be linked to each other to form a substituted or unsubstituted ring;

the R is _z Selected from the group consisting of alkyl groups with one or more deuterium, C1-C6, -Si (R) ₄ ) ₃ A substituted or unsubstituted group of any of the following: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzocyclobutanyl, benzocyclopentane ylBenzocyclohexenyl, benzocycloheptyl, benzocyclopentenyl, benzocyclohexenyl, benzofuranyl, or benzothienyl;

7. An organic electroluminescent device as claimed in claim 1, wherein Ar ₄ -Ar ₆ Are the same or different from each other, and are selected from any one of the structures shown below;

the t is ₂ Selected from CH or N atoms;

The R is _z Selected from the group consisting of alkyl groups with one or more deuterium, C1-C6, -Si (R) ₄ ) ₃ A substituted or unsubstituted group of any of the following: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclopentenyl, benzocyclohexenyl, benzofuranyl orBenzothienyl;

8. An organic electroluminescent device as claimed in claim 1, wherein the L ₄ -L ₆ Are the same or different from each other, and are selected from any one of single bonds or structures shown below and combinations thereof;

/>

the R is ₉ Are identical or different from each other and are selected from hydrogen, deuterium, -Si (R) ₄ ) ₃ Or any one of the following groups substituted or unsubstituted with one or more deuterium, C1-C6 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, benzocyclopentyl, benzocyclohexenyl, benzocycloheptyl, benzofuranyl or benzothienyl;

9. An organic electroluminescent device according to claim 1, wherein the hole transport region is selected from any one of the following structures;

/>

10. An organic electroluminescent device according to claim 1, wherein the electron transport region is selected from any one of the following structures;

/>