An amine compound, an organic electroluminescence element, and a consumer electronic device

Abstract

The application relates to the technical field of organic electroluminescent materials, in particular to an amine-based compound, an organic electroluminescent element and a consumer electronic device.The structural formula of the amine-based compound containing a noradamantyl group is shown as formula (I); the compound is applied in the organic electroluminescent element, and the driving voltage can be remarkably reduced, the luminous efficiency and the service life are improved;

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescent materials, in particular to an amine-based compound, an organic electroluminescent element and a consumer electronic device. BACKGROUND

[0002] The substances used in the organic electroluminescent element are mostly pure organic substances or organic metal complexes formed by complexing organic substances with metals, and can be classified as hole injectors, hole transporters, light emitters, electron transporters, electron injectors, etc. according to the use. Here, as the hole injectors or hole transporters, organic substances with relatively small ionization energy are mainly used, and as the electron injectors or electron transporters, organic substances with relatively large electronegativity are mainly used. In addition, the substances used as the light-emitting auxiliary layer preferably satisfy the following characteristics.

[0003] First, the substances used in the organic electroluminescent element need to have good thermal stability, because the Joule heat occurs due to the migration of charges inside the organic electroluminescent element. At present, the glass transition temperature of the material commonly used as the hole transport layer is low, so when driven at low temperature, the phenomenon of reduced light-emitting efficiency due to crystallization occurs. Second, in order to reduce the driving voltage, the organic substances adjacent to the cathode and the anode need to be designed to have a small charge injection barrier and a high charge mobility. Third, some charges are inevitably accumulated on the interface between the electrode and the organic layer and the interface between the organic layers due to the energy barrier, so substances with excellent electrochemical stability are needed.

[0004] The organic electroluminescent device generally includes an anode, a hole injection layer, a hole transport layer, an electroluminescent layer as an energy conversion layer, an electron transport layer and a cathode which are sequentially stacked. When a voltage is applied to the cathode and the anode, an electric field is generated between the two electrodes, and under the action of the electric field, the electrons on the cathode side move to the electroluminescent layer, and the holes on the anode side also move to the light-emitting layer. The electrons and holes combine to form excitons in the electroluminescent layer, and the excitons in the excited state release energy outward, and then the electroluminescent layer emits light. Therefore, the light-emitting efficiency of the light-emitting device depends on the utilization rate of the excitons and the light extraction efficiency. Low light extraction efficiency is one of the common problems of organic light-emitting devices, and the attenuation caused by the reflection of the different refractive indices of the organic materials between the layers becomes the main reason for the reduction of the device efficiency. In order to reduce this effect, an organic layer formed by a material with low refractive index needs to be formed on the side from which light is emitted. However, the organic materials with high carrier transportability and thermal stability derived from compounds with unsaturated bonds have a relatively high refractive index.

[0005] Based on the above reasons, the present application is proposed. SUMMARY

[0006] To solve the above problems, the present application provides an amine-based compound, an organic electroluminescent device and a consumer electronic device, which can reduce the refractive index, improve the material thermal stability and the ability to transport carriers, and the organic electroluminescent device prepared by using the amine-based compound can significantly reduce the driving voltage, improve the luminous efficiency and the service life.

[0007] Specifically, the present application provides the following technical solutions:

[0008] The present application first provides an amine-based compound, the structure of which is shown in formula (I):

[0009]

[0010] Among them,

[0011] L 1 , L 2 , L 3 Each independently selected from a single bond, a substituted or unsubstituted C6-C 60 arylene, a substituted or unsubstituted C2-C 60 heteroarylene, or a group consisting of the above-mentioned groups;

[0012] Ar 1 , Ar 2 Each independently selected from a substituted or unsubstituted C6-C 60 aryl, a substituted or unsubstituted C6-C 60 fused ring aryl, a substituted or unsubstituted C6-C 60 aromatic amine, a substituted or unsubstituted C2-C 60 heterocyclic aryl, or a group consisting of the above-mentioned groups;

[0013] R 1 represents one or more groups to saturated substitution, and the R 1 Each independently selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, a substituted or unsubstituted C1-C 40 alkyl, a substituted or unsubstituted C1-C 40 alkoxy, a substituted or unsubstituted C2-C 40 alkenyl, a substituted or unsubstituted C1-C 40 alkylthio, a substituted or unsubstituted C1-C 40 heteroalkyl, a substituted or unsubstituted C3-C 40 cycloalkyl, a substituted or unsubstituted C3-C 40 cycloalkenyl, a substituted or unsubstituted C6-C 60 aryl, a substituted or unsubstituted C6-C 60 aryloxy, a substituted or unsubstituted C6-C 60 arylthio, a substituted or unsubstituted C6-C60 an arylamine group, a substituted or unsubstituted C3-C 40 a silyl group, a substituted or unsubstituted C2-C 60 a heteroaryl group, or a group consisting of the above groups.

[0014] The amine-based compound according to the present application is represented by the above formula (I) and includes a basic skeleton formed by combining a noradamantyl group and an amine group. The present application has found that the compound represented by the above formula (I) is not only stable in electrochemistry, has excellent hole mobility and electron blocking ability, but also has a high glass transition temperature and excellent thermal stability, as compared with the known B-1 to B-4 structures.

[0015]

[0016] Thus, the amine-based compound according to the present application has excellent hole transport ability and electron blocking ability, and is therefore useful as a material for any one of a hole injection layer, a hole transport auxiliary layer, or an electron blocking layer of an organic layer of an organic electroluminescent element. It is preferable to be used as a material for any one of a hole transport auxiliary layer and an electron blocking layer, and it is more preferable to be used as a material for an electron blocking layer.

[0017] Specifically, the compound represented by the above formula (I) has a smaller refractive index, stronger hole transport ability and electron blocking ability, and is capable of exhibiting relatively high luminous efficiency and a high glass transition temperature, as compared with the known derivatives B-1 and B-2 containing a cyclohexyl group, B-3 containing an adamantyl group, and B-4 containing a norbornyl group, by virtue of the rigid noradamantyl fluorene derivative. Thus, in the case where the amine-based compound represented by the above formula (I) according to the present application is used for an organic electroluminescent element, not only excellent thermal stability and carrier transport ability, but also particularly electron blocking ability and luminous ability can be expected, and the driving voltage of the element can be reduced, the efficiency and the lifetime can be improved, and the like, and as a latest electron blocking layer material, an excellent efficiency increase due to a high triplet energy level can be exhibited by virtue of a triplet-triplet fusion effect.

[0018] An aryl group in the sense of the present application contains 6 to 60 carbon atoms, a heteroaryl group contains 2 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. In this case, two or more rings of the heteroaryl group can be attached to each other simply or in condensed form, further, a condensed form with an aryl group can also be contained. As non-limiting examples of such heteroaryl groups, mention can be made of six-membered monocyclic groups such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; polycyclic groups such as phenoxazinyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazolyl, carbazolyl; and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidyl and the like.

[0019] An alkyl group in the sense of the present application contains 1 to 40 carbon atoms, and straight-chain alkyl groups or alkyl groups with branches, in which the individual hydrogen atoms or -CH2- groups can also be substituted; alkenyl or alkynyl groups contain at least two carbon atoms, as non-limiting examples, alkyl, alkenyl or alkynyl groups are preferably understood to mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0020] Alkoxy groups preferably having 1 to 40 carbon atoms are understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.

[0021] The heteroalkyl group preferably has an alkyl group of 1 to 40 carbon atoms, and means a group in which a single hydrogen atom or -CH2- group is replaced by an oxygen, sulfur, or halogen atom, and as non-limiting examples, an alkoxy group, an alkylthio group, a fluorinated alkoxy group, a fluorinated alkylthio group, and particularly a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a t-butylthio group, a trifluoromethylthio group, a trifluoromethoxy group, a pentafluoroethoxy group, a pentafluoroethylthio group, a 2,2,2-trifluoroethoxy group, a 2,2,2-trifluoroethylthio group, an ethenyloxy group, an ethenylthio group, a propenyloxy group, a propenylthio group, a butenylthio group, a butenyloxy group, a pentenyloxy group, a pentenylthio group, a cyclopentenyloxy group, a cyclopentenylthio group, a hexenyloxy group, a hexenylthio group, a cyclohexenyloxy group, a cyclohexenylthio group, an ethynoxy group, an ethynylthio group, a propynoxy group, a propynylthio group, a butynoxy group, a butynylthio group, a pentynoxy group, a pentynylthio group, a hexynoxy group, and a hexynylthio group.

[0022] Generally, the cycloalkyl group, the cycloalkenyl group according to the present application can be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptyl group, a cycloheptenyl group, in which one or more -CH2- groups can be replaced by the above-mentioned groups; furthermore, one or more hydrogen atoms can also be replaced by a deuterium atom, a halogen atom, or a nitrile group.

[0023] The heterocycloalkyl group used in the present application means a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having an atomic number of 3 to 40. At this time, one or more carbons, preferably 1 to 3 carbons, in the ring are replaced by a heteroatom such as N, O, or S. As non-limiting examples thereof, there are tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like.

[0024] The fused ring aryl group used in the present application means a monovalent functional group obtained by removing one hydrogen atom from an aromatic hydrocarbon having a carbon number of 6 to 60 in which two or more rings are combined. At this time, the two or more rings can be simply attached to each other or attached in a condensed form. As non-limiting examples thereof, there are, for example, a phenanthryl group, an anthryl group, a fluoranthenyl group, a pyrenyl group, a triphenylenyl group, a perylenyl group, a chrysenyl group, a naphthacenyl group, a coronenyl group, a coronandyl group, and the like.

[0025] ​The arylamine group used in the present invention refers to an amine substituted with an aryl group having 6 to 60 carbon atoms. Non-limiting examples of arylamine groups include diphenylamine, N-phenyl-1-naphthylamine, and N-(1-naphthyl)-2-naphthylamine. A heteroarylamine group refers to an amine substituted with an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 2 to 60 carbon atoms. Non-limiting examples of heteroarylamine groups include N-phenylpyridin-3-amine, N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-2-amine, and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine.

[0026] The aryloxy group used in the present invention refers to R'O - The monovalent functional group represented by is an aryl group having a carbon number of 6 to 60. Non-limiting examples of such an aryloxy group include phenoxy, naphthyloxy, biphenyloxy and the like.

[0027] The alkylsilyl group used in the present invention refers to a silyl group substituted by an alkyl group having 1 to 40 carbon atoms, wherein the number of carbon atoms constituting the alkylsilyl group is at least 3. Non-limiting examples of the alkylsilyl group include trimethylsilyl and triethylsilyl. The arylsilyl group refers to a silyl group substituted by an aryl group having 6 to 60 carbon atoms.

[0028] The arylphosphino group used in the present invention refers to a diarylphosphino group substituted with an aryl group having 6 to 60 carbon atoms. Non-limiting examples of arylphosphino groups include diphenylphosphino and bis(4-trimethylsilylphenyl)phosphino. An aryloxyphosphino group is a diarylphosphino group in which the phosphorus atom is oxidized to its highest valence state.

[0029] The arylboryl group used in the present invention refers to a diarylboryl group substituted with an aryl group having 6 to 60 carbon atoms. Non-limiting examples of the arylboryl group include diphenylboryl and di(2,4,6-trimethylphenyl)boryl. The alkylboryl group refers to a dialkylboryl group substituted with an alkyl group having 1 to 40 carbon atoms. Non-limiting examples of the alkylboryl group include di-tert-butylboryl and diisobutylboryl.

[0030] Preferably, the aryl, heteroaryl or heterocyclic aryl can be phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, pyrenyl, phenyl, fluorenyl, peryl, fluoranthenyl, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, triphenylene, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, cis- or trans-indenocarbazolyl, indolocarbazolyl, benzofuranocarbazolyl, benzothiophenocarbazolyl, benzocarbazolyl, dibenzocarbazolyl, azadibenzo[g,iD]naphtho[2,1,8-cde]azulene, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroistrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzodibenzo[g,iD]naphtho[2,1,8-cde]azulene, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroistrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzodibenzo[g,iD]naphtho[2,1,8-cde]azulene Benzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo[5,6]quinolyl, benzo[6,7]quinolyl, benzo[7,8]quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, isoxazolyl, 1,2-thiazolyl , 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazatriphenylenyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorescein ring group, naphthyridinyl, azacarbazolyl, benzocarbolinyl, carbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3 -oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, quinazolinyl, benzothiadiazolyl or a group consisting of the above groups or a group derived from a combination of these systems.

[0031] In the present invention, the term "substituted or unsubstituted" means a group selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidine group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, a C1-C 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C1-C 40 Alkoxy, C3-C40 cycloalkyl, C3-C 40 cycloalkenyl, C6-C 60 aryl, C6-C 60 aryloxy, C6-C 60 arylthio, C6-C 60 heteroaryl, C2-C 1 substituted or unsubstituted, or substituted with two or more substituents selected from the above exemplified substituents.

[0032] Preferably, the amine compound is selected from any one of the structures of II-1 to II-8:

[0033]

[0034] wherein R 1 , L 2 , L 3 , Ar 1 , Ar 2 have the same meaning as defined in formula (I).

[0035] Further preferably, R 1 is selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, substituted or unsubstituted C1-C 40 alkyl, substituted or unsubstituted C3-C 40 cycloalkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 arylamino, or from the group consisting of the above groups.

[0036] Still further, R 1 is selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, isopentyl, hexyl, cyclohexyl, cycloheptyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, or from the group consisting of the above groups.

[0037] Still further, Ar 1 , Ar 2each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthryl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene, or a group consisting of the aforementioned groups.

[0038] As preferred, the L 1 , L 2 , L 3 each independently selected from a single bond, a group represented by III-1 to III-23 below, or a group consisting of the following groups:

[0039]

[0040] wherein the dotted line represents a connecting site of the group.

[0041] In the present application, the connecting position of the group represented by III-1 to III-23 above is not limited, and ortho, meta or para is all possible. The L 1 , L 2 , L 3 may each independently be substituted by one or more of deuterium, a halogen atom, a nitrile group, a C1-C20alkyl group, a C6-C20aryl group, a C2-C20heterocyclic aryl group, or a group consisting of the aforementioned groups, and when the substituent is plural, the plural substituents are the same or different from each other. 40 alkyl group, a C6-C20aryl group, a C2-C20heterocyclic aryl group, or a group consisting of the aforementioned groups, and when the substituent is plural, the plural substituents are the same or different from each other. 60 alkyl group, a C6-C20aryl group, a C2-C20heterocyclic aryl group, or a group consisting of the aforementioned groups, and when the substituent is plural, the plural substituents are the same or different from each other. 60 alkyl group, a C6-C20aryl group, a C2-C20heterocyclic aryl group, or a group consisting of the aforementioned groups, and when the substituent is plural, the plural substituents are the same or different from each other.

[0042] As preferred, the amine-based compound is selected from any one of structures II-1 to II-4;

[0043] R 1 is hydrogen or deuterium; L 1 is a single bond, L 2 , L 3 , Ar 1 , Ar 2 have the same meaning as defined in formula (I);

[0044]

[0045]

[0046] The present application can have a lower HOMO or a higher LUMO by adjusting the position of a substituent and the kind of a substituent, thereby enabling the compound to exhibit high hole-transporting property and electron-blocking property in an organic electroluminescent device.

[0047] In addition, the amine-based compound represented by Formula (I) of the present application can have a variety of substituted or unsubstituted Ar 1 and Ar 2 , especially aryl and / or heteroaryl, and the molecular weight of the compound is significantly increased, thereby increasing the glass transition temperature, thereby having higher thermal stability than conventional light-emitting materials. Accordingly, the performance and life characteristics of an organic electroluminescent device including the compound according to the present application can be greatly improved. The organic electroluminescent device having such improved performance and life characteristics can ultimately maximize the performance of a full-color organic light-emitting panel.

[0048] As a preferred, the amine-based compound is selected from any one of the compounds represented by Formulas D100 to D225:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] wherein, each of *—X—* is independently selected from *—O—*, *—S—* or one of the following structures:

[0056]

[0057] *— and —* represent a bond.

[0058] The present application also provides an organic electroluminescent material, the raw material of which includes the amine-based compound; the organic electroluminescent material has the ability of carrier transport and the ability of electron blocking.

[0059] The present application also provides the use of the amine-based compound in the preparation of an organic electroluminescent device.

[0060] The present application further provides an organic electroluminescence element comprising: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; wherein the material of at least one of the organic layers or the capping layer comprises the amine-based compound.

[0061] The organic electroluminescence element comprises a cathode, an anode, and at least one light-emitting layer. In addition to these layers, the organic electroluminescence element can comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers, and / or charge-generation layers. An intermediate layer having, for example, an exciton-blocking function can likewise be introduced between two light-emitting layers. It should be noted, however, that not all of these layers need necessarily be present. The organic electroluminescence device described here can comprise one light-emitting layer, or it can comprise a plurality of light-emitting layers. That is to say, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. A system having three light-emitting layers is particularly preferred, wherein the three layers can exhibit blue, green, and red emission. If there is more than one light-emitting layer, at least one of these layers comprises, according to the application, the amine-based compound of the present application.

[0062] Further, the organic electroluminescence element according to the present application does not comprise a separate hole-injection layer and / or hole-transport layer and / or hole-blocking layer and / or electron-transport layer, i.e. the light-emitting layer is directly adjacent to the electron-blocking layer or the hole-transport layer or the anode, and / or the light-emitting layer is directly adjacent to the electron-transport layer or the electron-injection layer or the cathode.

[0063] In the further layers of the organic electroluminescence element according to the present application, in particular in the hole-injection and hole-transport layers and in the electron-injection and electron-transport layers, all materials can be used in the manner generally used according to the prior art. The person of ordinary skill in the art will thus be able to use all materials known for organic electroluminescence elements in combination with the light-emitting layer according to the present application without inventive step.

[0064] Furthermore, preference is given to an organic electroluminescence element, one or more layers of which are applied by means of a sublimation method, wherein the sublimation in a vacuum sublimation apparatus takes place at a pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. However, the initial pressure can also be even lower, for example less than 10 -7 Pa.

[0065] Preference is likewise given to an organic electroluminescence element, one or more layers of which are applied by means of an organic vapour phase deposition method or by means of carrier gas sublimation, wherein the sublimation takes place at a pressure of 10 -5The material is applied at a pressure of between 1 Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.

[0066] It is furthermore preferred that the organic electroluminescent element is produced from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, offset printing, light-induced thermal imaging, thermal transfer, inkjet printing or nozzle printing, of one or more layers. Solubility of the compounds is obtained, for example, by suitable substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. It is furthermore possible to use hybrid methods, in which one or more layers are applied from solution and one or more further layers are applied by vapour deposition.

[0067] These methods are generally known to the person of ordinary skill in the art and they can apply them without inventive skill to an organic electroluminescent element comprising a compound according to the application.

[0068] The application therefore also relates to a method for producing an organic electroluminescent element according to the application, at least one layer is applied by means of a sublimation method, and / or is characterised in that at least one layer is applied by means of an organic vapour phase deposition method or by means of carrier gas sublimation, and / or is characterised in that at least one layer is applied from solution by spin coating or by means of a printing method.

[0069] Further, the present application relates to a formulation comprising at least one amine-based compound according to the present application as indicated above. The same preferences as indicated above with respect to the organic electroluminescence element apply to the compounds according to the present application. In particular, the formulation can comprise, in addition to the amine-based compound, further compounds. For processing the amine-based compounds according to the present application from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds according to the present application are required. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents can be used with preference. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1 -methyl naphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methyl anisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1 -methylpyrrolidone, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropyl naphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1 -bis(3,4-dimethylphenyl)ethane, or a mixture of any two or more of these solvents.

[0070] Preferably, the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer or an electron blocking layer; wherein the hole transport layer or the electron blocking layer comprises the amine-based compound.

[0071] More preferably, the electron blocking layer comprises the amine-based compound.

[0072] The present application also provides a consumer electronic device comprising the organic electroluminescence element.

[0073] In addition, unless otherwise specified, the raw materials used in the present application can be purchased from commercial suppliers, and any range recited includes the end values and any value between the end values as well as any sub-range comprised between the end values or any value.

[0074] Based on the above technical solutions, the present application has the following beneficial effects:

[0075] The present application can reduce the refractive index of the molecule by increasing the proportion of saturated groups in the organic material by introducing a noradamantyl group into a triarylamine molecule, while increasing the hole mobility and electron blocking properties of the material. The amine compound represented by formula (I) can be applied to the organic layer of an organic electroluminescent element due to its hole mobility, electron blocking property, thermal stability, and low refractive index. In particular, when the amine compound represented by formula (I) of the present application is applied to an electron blocking layer or a hole transport layer, an organic electroluminescent element with lower driving voltage, higher efficiency, and longer lifetime than conventional electron blocking materials can be manufactured, and furthermore, a full-color display panel with improved performance and lifetime can be manufactured. BRIEF DESCRIPTION OF DRAWINGS

[0076] In order to more clearly illustrate the technical solutions of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings described below are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0077] Figure 1 is a schematic diagram of an organic light-emitting device 100 prepared in Test Example 1 provided by the present application. The drawing is not necessarily drawn to scale. The device 100 can include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111.

[0078] Figure 2 is a schematic diagram of an organic light-emitting device 200 with two light-emitting layers prepared in Test Example 1 provided by the present application. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 can be prepared by sequentially depositing the described layers. Since the most common OLED device has one light-emitting layer, and the device 200 has a first light-emitting layer and a second light-emitting layer, the light-emitting peaks of the first light-emitting layer and the second light-emitting layer can be overlapping or cross-overlapping or non-overlapping.

[0079] REFERENCE NUMERALS:

[0080] 100: Test Example 1 organic light emitting device; 101: substrate; 102: anode; 103: hole injection layer; 104: hole transport layer; 105: electron blocking layer; 106: light emitting layer; 107: hole blocking layer; 108: electron transport layer; 109: electron injection layer; 110: cathode; 111: cap layer (CPL).

[0081] 200: Test Example 2 organic light emitting device; 201: substrate; 202: anode; 203: hole injection layer; 204: hole transport layer; 205: first light emitting layer; 206: electron transport layer; 207: charge generation layer; 208: hole injection layer; 209: hole transport layer; 210: second light emitting layer; 211: electron transport layer; 212: electron injection layer; 213: cathode. DETAILED DESCRIPTION

[0082] In order to make the objects, technical solutions, and advantages of the present application clearer, the technical solutions in the present application will be described clearly and completely below with reference to the drawings in the present application. Obviously, the described embodiments are only some, but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0083] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods. Unless otherwise specified, the experimental materials and related equipment used in the following examples can be obtained through commercial channels. Unless otherwise specified, the percentages are all mass percentages.

[0084] The test instruments and methods for performance testing of OLED materials and elements in the following examples are as follows:

[0085] OLED element performance detection conditions:

[0086] Luminance and chromaticity coordinates: tested using a spectral scanner PhotoResearch PR-715;

[0087] Current density and driving voltage: tested using a digital source meter Keithley 2420;

[0088] Power efficiency: tested using a NEWPORT 1931-C.

[0089] Example 1

[0090] The present example provides an amine-based compound, compound D145, and a preparation method thereof, which comprises the following steps:

[0091] First step: preparation of intermediate Int-1

[0092]

[0093] Under nitrogen protection, 20.0 mmol of 2-bromobiphenyl sub-2 was dissolved in 60 mL of dry THF, cooled to -80°C, 22.0 mmol of 2.5M n-butyllithium n-hexane solution was added dropwise, stirred for 10 minutes, 22.0 mmol of noradamantane-9-one was added dropwise, stirred for 1 hour, raised to room temperature, 20 mL of 2M dilute hydrochloric acid aqueous solution was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the combined organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. The residue was dissolved in 60 mL of dichloromethane, cooled to 0°C, 30.0 mmol of boron trifluoride ether solution was added dropwise, stirred for 2 hours, raised to room temperature, stirred for 15 hours, 50 mL of water was added, the organic phase was separated, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. Purification was performed by silica gel column separation to obtain compound Int-1, colorless oil, yield 85%.

[0094] Second step: preparation of intermediate Int-2

[0095]

[0096] Under nitrogen protection, 79.4 mmol of Int-1 was dissolved in 80 mL of chloroform, 7.9 mmol of anhydrous iron bromide was added, stirred for 10 minutes, 87.3 mmol of bromine dissolved in chloroform was added dropwise, stirred for 10 hours, raised to reflux for 1 hour, lowered to room temperature, 50 mL of saturated sodium bisulfite aqueous solution was added, the organic phase was separated, the aqueous phase was extracted with chloroform, the combined organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. Purification was performed by silica gel column separation to obtain compound Int-2, white solid, yield 95%.

[0097] Third step: preparation of compound D145

[0098]

[0099] Under nitrogen protection, 24.0 mmol of intermediate Int-2, 20.0 mmol of sub-3, 30.0 mmol of sodium tert-butoxide, 0.01 mmol of Pd2(dba)3 catalyst, 0.02 mmol of Xantphos and 80 mL of toluene were stirred at 100°C for 15 hours, cooled to room temperature, diluted with 50 mL of water, extracted with toluene, collected the organic phase, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. Purification was performed by silica gel column separation to obtain compound D145;

[0100] X: C(CH3)2, yellow solid, yield: 85%, MS (MALDI-TOF): m / z = 632.3255 [M+H] + ; 1 HNMR (δ, CDC13): 8.27 (1H, s); 7.91-7.88 (2H, m); 7.75-7.71 (2H, m); 7.54-7.46 (6H, m); 7.40-7.28 (8H, m); 7.26-7.22 (2H, m); 7.20-7.16 (2H, m); 2.14-2.07 (2H, m); 1.82-1.73 (2H, m); 1.68 (6H, s); 1.58-1.49 (8H, m).

[0101] X: C(Ph)2, yellow solid, yield: 83%, MS (MALDI-TOF): m / z = 756.3566 [M+H] + ; 1 HNMR (δ, CDC13): 7.91-7.86 (4H, m); 7.75-7.71 (2H, m); 7.55-7.46 (7H, m); 7.42-7.32 (6H, m); 7.28-7.21 (6H, m); 7.17-7.06 (8H, m); 2.14-2.07 (2H, m); 1.82-1.72 (2H, m); 1.59-1.49 (8H, m).

[0102] X: FR(9,9-fluorenyl), yellow solid, yield: 81%, MS (MALDI-TOF): m / z = 754.3408 [M+H] + ; 1 HNMR (δ, CDC13): 7.92-7.85 (4H, m); 7.75-7.71 (2H, m); 7.54-7.45 (6H, m); 7.42-7.33 (6H, m); 7.29-7.21 (5H, m); 7.19-7.12 (6H, m); 7.17-7.15 (2H, m); 2.14-2.07 (2H, m); 1.82-1.72 (2H, m); 1.59-1.49 (8H, m).

[0103] X: NPh, yellow solid, yield: 84%, MS (MALDI-TOF): m / z = 681.3275 [M+H] + ; 1HNMR (δ, CDC13): 8.37 (1H, s); 8.15 (1H, s); 7.92-7.87 (2H, m); 7.75-7.71 (2H, m); 7.61-7.52 (7H, m); 7.50-7.42 (5H, m); 7.40-7.28 (7H, m); 7.19-7.14 (3H, m); 2.13-2.07 (2H, m); 1.82-1.72 (2H, m); 1.59-1.48 (8H, m).

[0104] Example 2

[0105] This example provides an amine compound, compound D220, which is prepared by the following steps:

[0106] First Step: Preparation of Intermediate Int-3

[0107]

[0108] Under nitrogen protection, 20.0 mmol of Int-1' (prepared according to the synthetic method of the first step of Reference Example 1) was dissolved in 60 mL of dry THF, cooled to -78°C, and 22.0 mmol of 2.5M n-butyllithium n-hexane solution was added dropwise. After stirring for 30 minutes, 24.0 mmol of trimethyl borate was added dropwise, and stirring was continued for 1 hour. The reaction mixture was allowed to warm to room temperature, 50 mL of 3M dilute hydrochloric acid aqueous solution was added dropwise, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried, filtered, and concentrated under reduced pressure. The residue was dispersed by stirring in 50 mL of petroleum ether, filtered, and the filter cake was washed with petroleum ether to obtain intermediate Int-3 as a white solid in a yield of 80%.

[0109] Second Step: Preparation of Intermediate Int-4

[0110]

[0111] Under nitrogen protection, 22.0 mmol of Int-3 was dissolved in 60 mL of toluene, and 20.0 mmol of sub-4, 60.0 mmol of anhydrous sodium carbonate, 0.02 mmol of Pd(PPh3)4 catalyst, 30 mL of ethanol, and 30 mL of water were added. The reaction mixture was stirred and warmed to reflux for 15 hours, and then allowed to cool to room temperature. 50 mL of water was added, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate, and the organic phase was washed with saturated brine, dried, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain compound Int-4 as a white solid in a yield of 84%.

[0112] Third Step: Preparation of Compound D220

[0113]

[0114] Int-4 (24.0 mmol) was dissolved in 60 mL of toluene under nitrogen protection, and then sub-5 (20.0 mmol), anhydrous sodium tert-butoxide (30.0 mmol), Pd2(dba)3 catalyst (0.02 mmol) and 10% tri-tert-butylphosphine toluene solution (0.04 mmol) were added. The reaction was stirred at 100°C for 15 hours, cooled to room temperature, diluted with 50 mL of water, extracted with toluene, collected the organic phase, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. Purification was performed by silica gel column chromatography to obtain compound D220, a yellow solid, yield: 87%, MS (MALDI-TOF): m / z = 674.3721 [M+H] + ; 1 HNMR (δ, CDC13): 7.86 (1H, s); 7.76-7.71 (3H, m); 7.65-7.62 (1H, m); 7.59 (1H, s); 7.55-7.44 (7H, m); 7.42-7.35 (4H, m); 7.28-7.22 (3H, m); 7.14 (1H, s); 7.08-7.05 (2H, m); 7.02-6.99 (1H, m); 2.49-2.41 (1H, m); 2.13-2.07 (2H, m); 1.93-1.78 (8H, m); 1.69-1.46 (10H, m); 1.39-1.30 (2H, m).

[0115] Examples 3 to 126

[0116] Referring to the above similar synthesis method, the following compounds shown in Table 1 were prepared:

[0117] Table 1

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] In the above embodiment, *—X—* is selected from *—O—*, *—S—* or one of the following structures:

[0128]

[0129] *— and —* represent connecting keys.

[0130] Test Example 1

[0131] An OLED element 100, such as Figure 1 As shown, the OLED element of this embodiment is a top-emitting element, comprising a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, an organic light-emitting layer 106 disposed on the electron blocking layer 105, a hole blocking layer 107 disposed on the organic light-emitting layer 106, an electron transport layer 108 disposed on the hole blocking layer 107, an electron injection layer 109 disposed on the electron transport layer 108, a cathode 110 disposed on the electron injection layer 109, and a capping layer 111 on the cathode. A method for preparing an OLED element that does not include the hole blocking layer 107 comprises the following steps:

[0132] 1) A glass substrate coated with an ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in an acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with an ultraviolet light cleaner for 10 minutes, and bombarded with a low-energy cation beam.

[0133] 2) Place the treated ITO glass substrate in a vacuum chamber and evacuate the chamber to a vacuum of less than 1×10 -5 Pa, metallic silver is evaporated on the above ITO film as the anode layer, and the thickness of the evaporated film is Continue to evaporate compounds HI01 and HI02 as hole injection layers, where HI02 is 3% of the mass of HI01 and the thickness of the evaporated film is

[0134] 3) Continue to evaporate the compound HTM on the hole injection layer to form a hole transport layer with a thickness of

[0135] 4) The compound represented by formula (I) of the present invention (D100 to D225 prepared in Examples 1 to 126) was continuously evaporated on the hole transport layer as an electron blocking layer, with a film thickness of

[0136] 5) continue to evaporate compound BH035 as host material and BD018 as dopant material on the electron blocking layer, BD018 is 10% of the mass of BH035, as the organic light emitting layer of the element, the film thickness of the obtained organic light emitting layer is

[0137] 6) continue to evaporate a layer of LiQ and compound ET052 as the electron transport layer of the element on the organic light emitting layer, wherein the compound ET052 is 50% of the mass of LiQ, and the evaporation film thickness is

[0138] 7) continue to evaporate a layer of LiF as the electron injection layer on the electron transport layer, and the evaporation film thickness is

[0139] 8) evaporate metal magnesium and silver as the transparent cathode layer of the element on the electron injection layer, the mass ratio of magnesium and silver is 1:10, and the evaporation film thickness is

[0140] 9) continue to evaporate a layer of CPD as the CPL layer of the element on the transparent cathode layer, and the evaporation film thickness is to obtain the OLED element provided by the present application.

[0141] The structure of the compound used in the above test example 1 is as follows:

[0142]

[0143]

[0144] Test Example 2

[0145] An organic electroluminescent element 200, the structure of which is as shown in Figure 2 , comprises a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The preparation method of the electroluminescent element 200 is referred to Test Example 1. In the corresponding layers of the device 200, similar materials to those described with respect to the device 100 can be used.

[0146] Comparative Example 1

[0147] The present comparative example provides an amine-based compound H01, the structural formula of which is as follows:

[0148]

[0149] According to the same procedure as in Test Example 1, the compound of formula (I) in step 4) was replaced by H01 to obtain Comparative Element 1.

[0150] The organic electroluminescent element prepared according to the above process was subjected to the following performance tests:

[0151] The driving voltage and current efficiency of the organic electroluminescent element prepared in Test Examples 1, 2 and Comparative Example 1 above were measured using a digital source meter and a luminance meter, and the lifetime of the element was measured. Specifically, the voltage was increased at a rate of 0.1 V per second, and the voltage at which the luminance of the organic electroluminescent element reached 1000 cd / m 2 was measured as the driving voltage, and the current density at this time was measured; the ratio of the luminance to the current density was the current efficiency; the LT95% lifetime test was as follows: using a luminance meter, the time for the luminance of the organic electroluminescent element to decay to 9500 cd / m 2 was measured as the driving voltage, and the current density at this time was measured; the ratio of the luminance to the current density was the current efficiency; the LT95% lifetime test was as follows: using a luminance meter, the time for the luminance of the organic electroluminescent element to decay to 9500 cd / m 2 was measured as the driving voltage, and the current density at this time was measured; the ratio of the luminance to the current density was the current efficiency; the LT95% lifetime test was as follows: using a luminance meter, the time for the luminance of the organic electroluminescent element to decay to 9500 cd / m

[0152] Table 2

[0153]

[0154]

[0155]

[0156]

[0157] As can be seen from Table 2, the OLED element prepared from the compound of the present application has a lower driving voltage, a significantly improved current efficiency, and a longer LT95% lifetime than Comparative Element 1, indicating that the amine-based compound of the present application is an excellent electron-blocking layer material.

[0158] The compound H01 in Comparative Example 1 differs from the amine-based compound of the present application in that H01 has a large steric hindrance due to the adamantane group, resulting in a high driving voltage and low efficiency. However, the compound of the present application has a reduced steric hindrance after the introduction of noradamantane, and the hole transport performance and exciton blocking performance are improved, resulting in a significantly reduced driving voltage, and thus the OLED element prepared from the compound of the present application has a more excellent light-emitting performance and a significantly improved element performance.

[0159] Although the present application has been described in detail with particular reference to the foregoing illustrative embodiments, it should be understood that variations and modifications of the application can be effected without departing from the spirit and scope of the application.

[0160] Finally, it should be noted that the above-mentioned embodiments are merely used to illustrate the technical solutions of the present application, rather than limit the present application; even though the present application has been described in detail with reference to the foregoing embodiments, those ordinarily skilled in the art should understand that the technical solutions recorded in the foregoing embodiments can be modified or equivalent replacements can be made to some technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A compound, characterized in that The compound is selected from any one of the following compounds of formulae D100-D225: wherein each *—X—* is independently selected from *—O—*, *—S—* or one of the following structures: *—and—* represent a connecting bond.

2. Use of the compound of claim 1 in the preparation of an organic electroluminescent element.

3. An organic electroluminescent element characterized by comprising the compound according to claim 1. It comprises: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; The organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light-emitting layer, an electron transport layer or an electron injection layer and an electron blocking layer; wherein the electron blocking layer comprises the compound of claim 1.

4. A consumer electronic device, characterized by It comprises the organic electroluminescent element of claim 3.

Images