An amine-based compound of a cycloalkyl group and use thereof

Abstract

This invention relates to the field of organic electroluminescent materials, and more particularly to a cycloalkyl amino compound and its application in electronic components and devices. The structural formula of the cycloalkyl amino compound is shown in Formula (I); the compound of Formula (I) provided by this invention has at least one cycloalkyl structure. Applying this compound to organic electroluminescent elements can significantly reduce the driving voltage, improve luminous efficiency, and extend lifetime.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials technology, and more particularly to a cycloalkyl amine compound and its application in organic light-emitting elements and electronic devices. Background Technology

[0002] The materials used in organic electroluminescent devices are mostly pure organic compounds or organometallic complexes formed by organic compounds and metals. Depending on their application, they can be classified as hole injectors, hole transporters, luminescent materials, electron transporters, and electron injectors. Here, organic compounds with relatively low ionization energies are mainly used as hole injectors or hole transporters, while organic compounds with high electronegativity are mainly used as electron injectors or electron transporters. Furthermore, the material used as the luminescent auxiliary layer preferably meets the following characteristics:

[0003] First, the materials used in organic light-emitting diodes (OLEDs) need good thermal stability because Joule heating occurs inside the OLED due to charge migration. Currently, the materials commonly used as hole transport layers have low glass transition temperatures, leading to crystallization and reduced luminous efficiency at low temperatures. Second, to reduce the driving voltage, the organic materials adjacent to the cathode and anode need to be designed with low charge injection barriers and high charge mobility. Third, energy barriers inevitably exist at the interfaces between the electrodes and organic layers, and between organic layers, resulting in the accumulation of some charge. Therefore, materials with excellent electrochemical stability are required.

[0004] Organic light-emitting diodes (OLEDs) generally consist of an anode, a hole injection layer, a hole transport layer, an electroluminescent layer (serving as an energy conversion layer), an electron transport layer, and a cathode, stacked sequentially. When a voltage is applied to the anode and cathode, an electric field is generated. Under the influence of this electric field, electrons on the cathode side move towards the electroluminescent layer, and holes on the anode side also move towards it. Electrons and holes combine in the electroluminescent layer to form excitons. These excitons, in an excited state, release energy, causing the electroluminescent layer to emit light. Therefore, the luminous efficiency of the device depends on the exciton utilization rate and the light extraction efficiency. Low light extraction efficiency is a common problem in organic light-emitting diodes, especially the attenuation caused by reflection due to the difference in refractive index between organic materials in the layers, which is the main reason for the reduced device efficiency. To reduce this effect, an organic layer made of a low-refractive-index material needs to be formed on the light-emitting side. However, organic materials, especially compounds derived from unsaturated bonds, have high refractive indices, while possessing high carrier transport and thermal stability.

[0005] Based on the above reasons, this invention introduces cycloalkylamines into triarylamines using cycloalkyl molecules with low refractive index, thereby increasing the proportion of saturated groups in organic materials, reducing the refractive index of molecules, and simultaneously improving the hole mobility and electron blocking properties of the materials. Summary of the Invention

[0006] The purpose of this invention is to provide a cycloalkyl amino compound that can reduce the refractive index, improve the thermal stability of materials and the ability to transport charge carriers. Organic electroluminescent devices prepared using this cycloalkyl amino compound can significantly reduce the driving voltage, improve luminous efficiency and lifetime. Another purpose of this invention is to provide applications of this compound.

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

[0008] This invention provides a cycloalkyl amino compound with the structural formula shown in formula (I):

[0009]

[0010] Where n is selected from integers from 0 to 5; X is selected from 0, S, CR 2 R 3 SiR 2 R 3 or NAr 3 ;

[0011] L 1 Choose C6-C with free single bond, substituted or unsubstituted. 60 aryl, or substituted or unsubstituted C2-C 60 Groups composed of heteroarylene groups;

[0012] R 1 R 4 Each independently represents one, two, or more saturated substitutions, R 1 R 2 R 3 R 4 Each is independently selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, substituted or unsubstituted C1-C. 40 Alkyl, substituted or unsubstituted C1-C 40 Alkoxy, substituted or unsubstituted C2-C 40 alkenyl, substituted or unsubstituted C1-C 40 Alkylthio, substituted or unsubstituted C1-C 40 Heteroalkyl, substituted or unsubstituted C3-C 40 Cycloalkyl, substituted or unsubstituted C3-C 40 Cycloalkenyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 aryloxy, substituted or unsubstituted C6-C 60 Arylthio, substituted or unsubstituted C6-C 60Aromatic amino group, substituted or unsubstituted C3-C 40 Silyl, substituted or unsubstituted C2-C 60 A group consisting of heteroaryl groups; any two or more adjacent R groups 1 R 2 R 3 R 4 They can be arbitrarily joined or fused to form substituted or unsubstituted rings;

[0013] Ar 1 Ar 2 Ar 3 Each can independently select either freely substituted or unsubstituted C6-C. 60 aryl, substituted or unsubstituted C6-C 60 Fused aryl, substituted or unsubstituted C6-C 60 Aromatic amino group, or substituted or unsubstituted C2-C 60 A group composed of heteroaryl groups.

[0014] The halogen atom or halogen used in this invention can be used interchangeably, and refers to fluorine, chlorine, bromine or iodine.

[0015] In the context of this invention, the term "ring" refers to a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle, formed by joining or cyclizing. A condensed ring refers to a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocycle, a condensed aromatic heterocycle, or a combination thereof.

[0016] Compared with the structures of previously known compounds B-1 to B-4, the compounds represented by formula (I) according to the present invention are not only electrochemically stable, with excellent hole mobility and electron blocking ability, but also have high glass transition temperature, low optical refractive index and excellent thermal stability.

[0017]

[0018] Therefore, the cycloalkyl amine compounds of the present invention exhibit excellent hole transport and electron blocking capabilities, and are thus suitable as materials for any one of the hole injection layer, hole transport auxiliary layer, or electron blocking layer in the organic layer of an organic electroluminescent element. Preferably, they are materials suitable for use as either a hole injection layer or an electron blocking layer; more preferably, they are materials suitable for use as a hole injection layer.

[0019] Specifically, the compounds of formula (I) of the present invention, through substitution or unsubstituted cycloalkylamine derivatives, exhibit lower refractive indices and stronger electron blocking capabilities compared to known cycloalkyl-containing derivatives B-1, B-2, B-3 and compound B-4 containing two triarylamine groups, thus displaying relatively high glass transition temperatures and thermal decomposition temperatures. Therefore, when the cycloalkylamine compounds of formula (I) of the present invention are used in organic electroluminescent devices, excellent thermal stability and carrier transport capabilities, especially electron blocking and light extraction capabilities, are expected. Furthermore, the device's driving voltage can be reduced, efficiency and lifetime improved, and as a novel electron blocking layer material, it exhibits excellent efficiency gains due to the triplet-triplet fusion effect caused by the high triplet energy level.

[0020] Furthermore, the cycloalkyl amino compounds of formula (I) of the present invention are derived by comprising substituent R 1 cycloalkylamine group and L 1 NAr 1 Ar 2 The introduction of [a specific compound] allows for the adjustment of HOMO and LUMO energy levels based on the type of substituent, resulting in either a lower HOMO or a higher LUMO. Organic electroluminescent devices using such compounds exhibit the highest hole transport and electron blocking properties.

[0021] Furthermore, the cycloalkyl amino compounds of formula (I) of the present invention are introduced into various substituted or unsubstituted Ar groups of the above-mentioned basic skeleton. 1 Ar 2 and / or Ar 3 Especially with aryl and / or heteroaryl compounds, the molecular weight of the compounds increases significantly, thereby raising the glass transition temperature and resulting in higher thermal stability compared to conventional luminescent materials. Therefore, the performance and lifetime characteristics of organic electroluminescent elements containing the compounds according to the present invention can be greatly improved. Such improved performance and lifetime characteristics ultimately enable the maximization of the performance of full-color organic light-emitting panels.

[0022] In this invention, the aryl group contains 6 to 60 carbon atoms, and the heteroaryl group contains 2 to 60 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O, or S. In this case, the two or more rings of the heteroaryl group can simply attach to each other or in a condensed form, and further, it may also include forms condensed with the aryl group. Non-limiting examples of such heteroaryl groups include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathiyl, indoleazinyl, indoleyl, purine, quinolinyl, benzothiazolyl, and carbazoleyl; and 2-furanyl, N-imidazolyl, 2-isooxazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0023] For the purposes of this invention, alkyl refers to a straight-chain alkyl group containing 1 to 40 carbon atoms, wherein a single hydrogen atom or a -CH2- group may be substituted; alkenyl or ynyl refers to an alkyl group containing at least two carbon atoms. As a non-limiting example, alkyl, alkenyl or ynyl is preferably considered to refer to the following groups: 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, penynyl, hexynyl, hepynyl or ocynyl.

[0024] The preferred alkoxy group has 1 to 40 carbon atoms and is considered to be alkoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexoxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy, and 2,2,2-trifluoroethoxy.

[0025] Heteroalkyl groups are preferably alkyl groups having 1 to 40 carbon atoms, meaning groups in which a single hydrogen atom or -CH2- group is replaced by an oxygen, sulfur, or halogen atom. As non-limiting examples, alkoxy, alkathio, fluoroalkoxy, fluoroalkathio, especially methyl thio, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methyl thio, ethyl thio, n-propyl thio, isopropyl thio, n-butyl thio, isobutyl thio, sec-butyl thio, tert-butyl thio, and trifluoromethyl thio 2,2,2-trifluoroethoxy, pentafluoroethoxy, pentafluoroeththio, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroeththio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butenthio, butenoxy, penenoxy, penenthio, cyclopentenoxy, cyclopententhio, hexenoxy, hexenthio, cyclohexenoxy, cyclohexenthio, acetylenoxy, acetylenthio, propylenoxy, propylenthio, butylenoxy, butylenthio, penylenoxy, penylenthio, hexylenoxy, hexylenthio.

[0026] Generally, the cycloalkyl and cycloalkenyl groups according to the present invention can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, or cycloheptenyl, wherein one or more -CH2- groups can be replaced by the above groups; in addition, one or more hydrogen atoms can be replaced by deuterium atoms, halogen atoms, or nitrile groups.

[0027] The heterocyclic alkyl group used in this invention refers to a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon with 3 to 40 atomic nuclei. In this case, one or more carbon atoms in the ring, preferably 1 to 3 carbon atoms, are replaced by heteroatoms such as N, O, or S. Non-limiting examples include tetrahydrofuranyl, tetrahydrothiophenyl, morpholinyl, and piperazineyl.

[0028] The fused-ring aryl group used in this invention refers to a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon with 10 to 60 carbon atoms, which consists of two or more rings. In this case, the two or more rings can be simply attached to each other or attached in a condensed form. Non-limiting examples include phenanthrene, anthracene, fluoranthracene, pyrene, triphenylene, perylene, etc. Base, etc.

[0029] The aromatic amine group used in this invention refers to an amine substituted with an aryl group having 6 to 60 carbon atoms. Non-limiting examples of aromatic amine groups include diphenylamine, N-phenyl-1-naphthylamine, and N-(1-naphthyl)-2-naphthylamine. The heteroaryl amine group refers to an amine substituted with an aryl group having 6 to 60 carbon atoms or a heteroaryl group having 2 to 60 carbon atoms. Non-limiting examples of heteroaryl amine 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-fluorene-2-amine.

[0030] The aryl group used in this invention refers to R'O - The monovalent functional group represented by R' is an aryl group with 6 to 60 carbon atoms. Non-limiting examples of such aryl groups include phenoxy, naphthoxy, and biphenoxy groups.

[0031] The alkylsilyl group used in this invention refers to a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and the alkylsilyl group has at least 3 carbon atoms. Non-limiting examples of alkylsilyl groups include trimethylsilyl and triethylsilyl. Arylsilyl refers to a silyl group substituted with an aryl group having 6 to 60 carbon atoms.

[0032] The arylphospho group used in this invention refers to a diarylphospho group substituted with an aryl group having 6 to 60 carbon atoms. Non-limiting examples of arylphospho groups include diphenylphospho and di(4-trimethylsilylphenyl)phospho. Aryloxophospho is formed when the phosphorus atom of a diarylphospho group is oxidized to its highest valence state.

[0033] The arylboryl group used in this invention refers to a diarylboryl group substituted with an aryl group having 6 to 60 carbon atoms. Non-limiting examples of arylboryl groups include diphenylboryl and di(2,4,6-trimethylphenyl)boryl. Alkylboryl groups refer to dialkylboryl groups substituted with an alkyl group having 1 to 40 carbon atoms. Non-limiting examples of alkylboryl groups include di-tert-butylboryl and diisobutylboryl.

[0034] Preferably, the aryl, heteroaryl, or heterocyclic aryl group is selected from phenyl, naphthyl, anthracel, benzo[a]anthrayl, phenanthryl, pyrene, etc. alkyl, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, amphyl, terphenyl, trimerphenyl, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthrene, triphenylene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorenyl, cis or trans indo[a]carbazolyl, indole[a]carbazolyl, benzo[a]furan[a]carbazolyl, benzo[a]thio[a]carbazolyl, benzo[a]carbazolyl, dibenzo[a]carbazolyl, azadibenzo[g,iD]naphtho[2,1,8-cde]azine, trimerinyl, isotrimerinyl, spirotrimerinyl, spiroisotrimerinyl, furanyl, benzo[a]furanyl, isobenzo[a]furanyl Dibenzofuranyl, thiophenyl, benzothiophenyl, isobenzothiophenyl, dibenzothiophenyl, pyrroleyl, indoleyl, isoindoleyl, carbazoyl, pyridyl, quinolinyl, isoquinolinyl, acridineyl, phenanthridineyl, benzo[5,6]quinolinyl, benzo[6,7]quinolinyl, benzo[7,8]quinolinyl, phenothiazinyl, phenotoxazinyl, pyrazolyl, indazoleyl, imidazoleyl, benzimidazoleyl, naphthimazoleyl, phenanthimazoleyl, pyridiniumimazoleyl, pyraziniumimazoleyl, quinoxoliniumimazoleyl, oxazolyl, benzoxoxazolyl, naphthoxazolyl, anthraquinonexazolyl, phenanthoxazolyl, isoxazolyl, 1,2- Thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthrayl, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenoxazinyl, phenthiazinyl, fluoresceinyl, naphridinyl, azacarbazolyl, benzocarbaolinyl, carbaolinyl, phenanthrolinel, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1 The group consisting of or derived from the group consisting of 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-tetraazinyl, 1,2,3,4-tetraazinyl, 1,2,3,5-tetraazinyl, purine, pteridine, indazinyl, quinazolinyl, and benzothiadiazolyl.

[0035] As is preferred, the cycloalkyl amino compound represented by formula (I) of the present invention is selected from the group consisting of the following structures:

[0036]

[0037] Among them, R 1 R 4 L 1 X, n, Ar1 Ar 2 The meaning is the same as the definition of formula (I).

[0038] Furthermore, X is selected from O, S, and CR. 2 R 3 , or NAr 3 .

[0039] Furthermore, the R 1 R 4 Choose from hydrogen, deuterium, fluorine, nitrile, substituted or unsubstituted C1-C groups. 40 Alkyl, substituted or unsubstituted C3-C 40 Groups consisting of cycloalkyl groups.

[0040] Furthermore, the R 2 R 3 Each independently selects either freely 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 A group composed of aromatic amino groups.

[0041] Furthermore, the Ar 1 Ar 2 Ar 3 Each can independently select either freely substituted or unsubstituted C6-C. 60 aryl, or substituted or unsubstituted C2-C 60 A group composed of heteroaryl groups.

[0042] Furthermore, n is selected from 0, 1, or 2.

[0043] Preferably, the R 1 R 4 Each is independently 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 triphenylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophene.

[0044] Preferably, the R 2 R 3 Each is independently selected from the group consisting of methyl, ethyl, substituted or unsubstituted phenyl, and substituted or unsubstituted fluorenyl groups.

[0045] Preferably, the Ar 1 Ar 2 Ar 3 Each of the following groups is independently selected: substituted or unsubstituted phenyl, substituted or unsubstituted diphenyl, substituted or unsubstituted triphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted triphenylene, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted fluoranthyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl.

[0046] According to an embodiment of the present invention, the R 1 R 4 Choose from the group consisting of hydrogen, deuterium, nitrile, methyl, tert-butyl, cyclopentyl, and cyclohexyl.

[0047] According to an embodiment of the present invention, the R 2 R 3 Each is independently selected from groups consisting of methyl, substituted or unsubstituted phenyl groups.

[0048] Preferably, the L 1 Each is independently selected from either a single bond or any one of formulas (20) to (35), and the specific structural formulas of formulas (20) to (35) are as follows:

[0049]

[0050] Wherein, Y is selected from O, S, SO, SO2, Se, and CR. ’ R”, ​​SiR ’ R” or NAr ’ ;

[0051] R represents one, two, or more saturated substitutions, each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidine, hydrazine, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonate, phosphate or its phosphate, C1-C 60 Alkyl, C2-C 60 alkenyl, C2-C 60 alkynyl group, C1-C 60 alkoxy groups, C3-C 60 Cycloalkane group, C3-C 60 Cycloolefinic, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 aryloxy, substituted or unsubstituted C6-C 60aryl sulfide group, or substituted or unsubstituted C2-C 60 Groups composed of heteroaryl groups;

[0052] R ’ Each of "R" is independently selected from C1-C. 60 Alkyl, C1-C 60 heteroalkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 Aromatic amino group, or substituted or unsubstituted C2-C 60 Groups composed of heteroaryl groups, R ’ R and R can optionally be joined or fused to form one or more additional substituted or unsubstituted rings, the formed rings containing or not containing one or more heteroatoms N, P, B, O or S; preferably, R ’ "R" represents hydrogen, methyl, phenyl, or fluorene.

[0053] Ar ’ Choose freely from C1 to C 60 Alkyl, C1-C 60 heteroalkyl, C3-C 60 cycloalkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C6-C 60 Fused aryl, substituted or unsubstituted C6-C 60 Aromatic amino group, or substituted or unsubstituted C2-C 60 Groups consisting of heterocyclic aryl groups; preferably, Ar ’ It can be methyl, ethyl, phenyl, biphenyl, or naphthyl;

[0054] The dashed lines represent the bonding sites of the functional groups.

[0055] In this context, the dashed lines represent the bonding sites of groups. Therefore, the bonding positions of the groups shown in equations (20) to (35) are not limited; ortho, meta, and para are all acceptable. The L mentioned above... 1 Each can be independently selected from hydrogen, deuterium, halogen atom, nitrile group, C1-C 40 Alkyl, C6-C 60 Aryl and C2-C 60 The group of heterocyclic aryl groups is substituted with one or more substituents. In this case, when there are multiple substituents, it is preferred that the multiple substituents are the same or different from each other.

[0056] In this invention, the term "substituted or unsubstituted" refers to a group selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidine, hydrazine, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonate, phosphate or its phosphate, C1-C 40 Alkyl, C2-C 40alkenyl, C2-C 40 Alkyne group, C1-C 40 Alkoxy, C3-C 40 cycloalkyl, C3-C 40 Cycloalkenyl, C6-C 60 Aryl, C6-C 60 Aryloxy group, C6-C 60 Aryl sulfide groups and C2-C 60 The heterocyclic aryl group is substituted or unsubstituted by one or more substituents, or is substituted or unsubstituted by a substituent formed by linking two or more substituents of the substituents exemplified above.

[0057] Preferably, the cycloalkyl amino compound is selected from compounds represented by formulas D100-D207:

[0058]

[0059]

[0060]

[0061]

[0062]

[0063] Wherein, *—X—* and *—T—* are each independently selected from *—O—*, *—S—*, or one of the structures shown below:

[0064]

[0065] *— and —* represent connector keys.

[0066] The present invention also provides a low-refractive-index organic electroluminescent material, the raw materials of which include the above-mentioned cycloalkyl amine compounds; the organic electroluminescent material including the cycloalkyl amine compounds of the present invention has carrier transport capability and electron blocking capability.

[0067] The present invention also provides the application of the above-described cycloalkyl amine compounds in the preparation of organic electroluminescent elements.

[0068] The present invention also provides an organic electroluminescent 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 at least one of the organic layers or capping layers (CPL) comprises a cycloalkyl amine compound as described above.

[0069] The organic electroluminescent element comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, it may also comprise other layers, such as, 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, exciton blocking functionality may also be introduced between two emitting layers. However, it should be noted that each of these layers is not necessarily required. The organic electroluminescent device described herein may comprise one emitting layer, or it may comprise multiple emitting layers. That is, a variety of luminescent compounds capable of emitting light are used in the emitting layers. A system having three emitting layers is particularly preferred, wherein the three layers can exhibit blue, green, and red light emission. If more than one emitting layer is present, according to the invention, at least one of these layers comprises a cycloalkyl amino compound of the invention.

[0070] Furthermore, the organic electroluminescent element according to the present invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, that is, the light-emitting layer is directly adjacent to the electron blocking layer or hole transport layer or anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.

[0071] In the other layers of the organic electroluminescent element according to the invention, particularly in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in accordance with the manner commonly used in the prior art. Those skilled in the art will therefore be able to use all materials known about organic electroluminescent elements in combination with the light-emitting layers according to the invention without inventive effort.

[0072] Furthermore, the following organic electroluminescent elements are preferred, wherein one or more layers are applied by means of a sublimation method, wherein in a vacuum sublimation apparatus at a temperature below 10 -5 Pa, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of Pa. However, the initial pressure may be even lower, for example, below 10 Pa. -7 Pa.

[0073] Similarly, the following organic electroluminescent elements are preferred, wherein one or more layers are applied by means of organic vapor deposition or by means of carrier gas sublimation, wherein, in 10 -5 The material is applied at a pressure between Pa and 1 Pa. A particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is therefore structured.

[0074] Furthermore, the following organic electroluminescent elements are preferred, which produce one or more layers from solution, for example by spin coating, or by any desired printing method such as screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, inkjet printing, or nozzle printing. Soluble compounds, for example, obtained through appropriate substitution, are also preferred. These methods are particularly suitable for oligomers, dendritic macromolecules, and polymers. Additionally, mixing methods are feasible, in which one or more layers are applied from solution and one or more additional layers are applied by vapor deposition.

[0075] These methods are generally known to those skilled in the art, and they can be applied to organic electroluminescent elements containing compounds according to the invention without any inventive effort.

[0076] Therefore, the present invention also relates to a method of manufacturing an organic electroluminescent element according to the invention, wherein at least one layer is applied by means of a sublimation method, and / or characterized by applying at least one layer by means of an organic vapor deposition method or by means of carrier gas sublimation, and / or characterized by applying at least one layer from a solution by spin coating or by means of a printing method.

[0077] Furthermore, the present invention relates to an amino compound comprising at least one of the cycloalkyl groups of the present invention as described above. The same preferred embodiments as noted above regarding organic electroluminescent elements apply to the compounds of the present invention. In particular, other compounds may preferably be included in addition to the cycloalkyl amino compounds. Processing the compounds of the present invention from a liquid phase, such as by spin coating or printing, requires formulations for processing the compounds. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents may be preferred. Suitable and preferred solvents include, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methyl anisole, 4-methyl anisole, 3,4-dimethyl anisole, 3,5-dimethyl anisole, acetophenone, α-terpenes. Alcohol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-methylisopropylbenzene, phenethyl ether, 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-isopropylnaphthalene, pentabenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0078] Preferably, the organic layer includes 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.

[0079] Furthermore, the hole injection layer, hole transport layer, capping layer, or electron blocking layer comprises a cycloalkyl amine compound of the present invention.

[0080] Furthermore, the hole injection layer comprises a cycloalkyl amine compound of the present invention.

[0081] Furthermore, the coating layer comprises a cycloalkyl amine compound of the present invention.

[0082] The present invention also provides a consumer electronic device comprising the organic electroluminescent element described above.

[0083] The consumer electronic device described in this invention can be one of the following products: flat panel display, computer monitor, medical monitor, television set, signboard, lamp for internal or external lighting and / or signaling, head-up display, fully transparent or partially transparent display, flexible display, laser printer, telephone, cellular phone, tablet computer, tablet phone, personal digital assistant (PDA), wearable device, laptop computer, digital camera, camcorder, viewfinder, microdisplay with a diagonal of less than 2 inches, 3-D display, virtual reality or augmented reality display, vehicle, video wall comprising multiple displays tiled together, theater or stadium screen, phototherapy device, and signage.

[0084] In addition, unless otherwise specified, all raw materials used in this invention can be obtained commercially available. Any range described in this invention includes the end value and any value between the end values, as well as any sub-range formed by the end value or any value between the end values.

[0085] The beneficial effects achieved by this invention are as follows:

[0086] The cycloalkyl amine compounds of formula (I) provided by this invention can be applied to the organic layers and / or capping layers of organic electroluminescent elements due to their hole mobility, electron blocking properties, thermal stability, and low optical refractive index. In particular, when the cycloalkyl amine compounds of formula (I) of this invention are applied to electron blocking layers, hole injection layers, or capping layers, organic electroluminescent elements with lower driving voltages, higher efficiency, and longer lifespans compared to conventional materials can be manufactured. Furthermore, full-color display panels with improved performance and lifespan can also be manufactured. Attached Figure Description

[0087] Figure 1 A schematic diagram of an organic light-emitting device 100 is shown. The diagram is not necessarily drawn to scale. Device 100 may 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, wherein the capping layer may include a light extraction layer (LEL) 111a and a sealing layer 111b. Device 100 may be fabricated by sequentially depositing the described layers.

[0088] Figure 2A schematic diagram of an organic light-emitting device 200 with two light-emitting layers is shown. 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. Other layers, such as the capping layer (CPL) in device 100, can be stacked on top of the cathode 213. Device 200 can be fabricated by sequentially depositing the described layers. Because most common OLED devices have one light-emitting layer, and device 200 has a first light-emitting layer and a second light-emitting layer, the emission peaks of the first and second light-emitting layers can be overlapping, cross-overlapping, or non-overlapping. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 Provide an example of how to add layers from the structure of device 100. Detailed Implementation

[0089] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the invention.

[0090] In the description of this invention, unless otherwise stated, "a plurality of" means two or more; the terms "upper," "lower," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the invention.

[0091] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods. Unless otherwise specified, the experimental materials and related equipment used in the following embodiments are commercially available, and all percentages are by mass.

[0092] The following embodiments use the following testing instruments and methods for performance testing of OLED materials and components:

[0093] OLED component performance testing conditions:

[0094] Luminosity and chromaticity coordinates: tested using a PhotoResearch PR-715 spectral scanner;

[0095] Current density and drive voltage: tested using a Keithley 2420 digital source meter;

[0096] Power efficiency: Tested using NEWPORT 1931-C.

[0097] Example 1

[0098] The preparation method of compound D110, taking X=O as an example, includes the following steps:

[0099] Step 1: Preparation of intermediate Int-1

[0100]

[0101] Under nitrogen protection, 20.0 mmol of 1-naphthol and 50 mL of hexafluoroisopropanol were mixed and heated to reflux. 20.0 mmol of titanium tetrachloride was added dropwise, followed by the slow addition of 20.0 mmol of sub-2 dissolved in hexafluoroisopropanol. The mixture was stirred for 15 hours, cooled to room temperature, and 150 mL of saturated ammonium chloride aqueous solution was added. The mixture was extracted with dichloromethane, and the organic phase was collected, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was then purified by silica gel column chromatography to give compound Int-1 as a yellow solid, with a yield of 78%.

[0102] Step 2: Preparation of intermediate Int-2

[0103]

[0104] Under nitrogen protection, 20.0 mmol of Int-1 was dissolved in 60 mL of dichloromethane, and 22.0 mmol of N-bromosuccinimide (NBS) was added in portions. The mixture was stirred for 2 hours, and 50 mL of water was added. The organic phase was separated and washed twice with water. The organic phase was collected, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was purified by silica gel column chromatography to give compound Int-2 as a yellow solid with a yield of 94%.

[0105] Step 3: Preparation of compound D110

[0106]

[0107] 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, 0.04 mmol of 10% tri-tert-butylphosphine toluene solution, and 80 mL of toluene were mixed, heated to 100 °C, and stirred for 15 hours. The mixture was then cooled to room temperature, diluted with 50 mL of water, extracted with toluene, and the organic phase was collected, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was purified by silica gel column chromatography to give compound D110 (X=O), a yellow solid, in 87% yield. 1HNMR (δ, CDCl3): 8.09~8.03(2H,m); 7.68~7.59(6H,m); 7.50~7.45(4H,m); 7.40~7.34(2H,m); 7.26~7.22(4H,m) ); 7.12~7.08(4H,m); 7.05(1H,s); 3.25~3.13(2H,m); 2.86~2.69(2H,m); 2.05~1.94(2H,m); 1.92~1.75(2H,m).

[0108] Referring to the above examples, compound D110 (X = S) was prepared by replacing 1-naphthiophenol in the first step of Example 1 with 1-naphthiophenol. The resulting product was a yellow solid with a yield of 83%. 1 HNMR (δ, CDCl3): 8.14~8.12(2H,m); 7.62~7.58(4H,m); 7.52~7.45(6H,m); 7.40~7.34(2H,m); 7.26~7.22(4H,m) ); 7.15(1H,s); 7.12~7.08(4H,m); 3.79~3.63(2H,m); 3.53~3.36(2H,m); 1.98~1.82(2H,m); 1.79~1.62(2H,m).

[0109] Example 2

[0110] The preparation method of compound D186, taking X=NPh as an example, includes the following steps:

[0111] Step 1: Preparation of intermediate Int-3

[0112]

[0113] Under nitrogen protection, 30.0 mmol of sub-4, 30.0 mmol of cyclohexanone, and 60 mL of glacial acetic acid were mixed, heated to 70 °C, and stirred for 1 hour. After cooling to room temperature, 60 mL of 48% hydrobromic acid aqueous solution was added, and the mixture was heated to 100 °C and stirred for 15 hours. After cooling to room temperature, the mixture was filtered, and the filter cake was washed with water and then with a saturated sodium carbonate aqueous solution to obtain intermediate Int-3, yield: 90%.

[0114] Step 2: Preparation of intermediate Int-4

[0115]

[0116] Under nitrogen protection, 20.0 mmol of Int-3 and 24.0 mmol of iodobenzene were dissolved in 80 mL of dry toluene. Then, 80.0 mmol of anhydrous potassium carbonate, 2.0 mmol of cuprous iodide, and 6.0 mmol of N,N'-dimethylethylenediamine were added. The mixture was heated to reflux and stirred for 15 hours. After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was then purified by silica gel column chromatography to give compound Int-4 as a yellow solid, with a yield of 88%.

[0117] Step 3: Preparation of compound D186

[0118]

[0119] Under nitrogen protection, 24.0 mmol of Int-4 was dissolved in 60 mL of toluene, followed by the addition of 20.0 mmol of sub-5, 30.0 mmol of anhydrous sodium tert-butoxide, 0.02 mmol of Pd2(dba)3 catalyst, and 0.04 mmol of a 10% tri-tert-butylphosphine toluene solution. The mixture was heated to 100 °C and stirred for 15 hours. After cooling to room temperature, 50 mL of water was added for dilution, and the mixture was extracted with toluene. The organic phase was collected, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was purified by silica gel column chromatography to give compound D186 (X = NPh) as a yellow solid, yield: 87%. 1 HNMR (δ, CDCl3): 7.94~7.92(1H,d); 7.74~7.70(2H,m); 7.64~7.58(3H,m) ;7.55~7.49(4H,m);7.46~7.39(4H,m);7.36~7.34(1H,d);7.24(1H,s);7 .19~7.14(4H,m); 7.09(1H,s); 7.01~6.97(2H,m); 3.23~3.07(2H,m); 2.6 4~2.46(3H,m); 1.88~1.67(6H,m); 1.61~1.46(6H,m); 1.40~1.29(2H,m).

[0120] Following the synthesis method described in Example 1 above, compounds of D186 (X=O and X=S) were prepared; X=O was a yellow solid, yield: 85%. 1HNMR (δ, CDCl3): 7.79~7.77(1H,d); 7.59(1H,s); 7.55~7.49(4H,m); 7.46 ~7.44(1H,m); 7.39~7.35(3H,m); 7.24(1H,s); 7.17~7.11(5H,m); 7.01~6 .97(2H,m); 3.08~2.92(2H,m); 2.87~2.71(2H,m); 2.61~2.52(1H,m); 2.0 9~1.98(2H,m); 1.96~1.79(4H,m); 1.61~1.46(6H,m); 1.40~1.29(2H,m).

[0121] X = S, yellow solid, yield: 84%. 1 HNMR (δ, CDCl3): 7.77~7.70(2H,m); 7.55~7.49(4H,m); 7.46~7.44(1H,m); 7.39~7.35(3H,m); 7.29~7.26(1H,d); 7.18~7. 12(4H,m); 7.09(1H,s); 7.01~6.97(2H,m); 3.62~3.38(4H,m); 2.61~2.51(1H,m); 2.04~1.46(12H,m); 1.40~1.29(2H,m).

[0122] Example 3

[0123] The preparation method of compound D193, taking X=CMe2 as an example, includes the following steps:

[0124] Step 1: Preparation of intermediate Int-5

[0125]

[0126] Under nitrogen protection, 22.0 mmol of sub-6 and 20.0 mmol of 1,4-dibromonaphthalene were dissolved in 40 mL of toluene, followed by the addition of 60.0 mmol of sodium carbonate, 0.01 mmol of Pd132, 20 mL of water, and 20 mL of ethanol. The mixture was heated to reflux and stirred for 12 hours. After cooling 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 phases were combined, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was then purified by silica gel column chromatography to give intermediate Int-5 as a yellow solid in 83% yield.

[0127] Step 2: Preparation of intermediate Int-6

[0128]

[0129] Under nitrogen protection, 20.0 mmol of Int-5 was dissolved in 50 mL of dry THF, cooled to 0 °C, and 22.0 mmol of 1 M methyl magnesium bromide THF solution was added dropwise. The mixture was then heated to room temperature and stirred for 1 hour. 50 mL of 2 M dilute hydrochloric acid aqueous solution was added, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The residue was dissolved in 100 mL of dichloromethane, and 30.0 mmol of pyridine chlorochromate was added. The mixture was stirred for 5 hours, filtered, and the filter cake was washed with dichloromethane. The filtrate was concentrated to dryness under reduced pressure and purified by silica gel column chromatography to give intermediate Int-6, a white solid, in 87% yield.

[0130] Step 3: Preparation of intermediate Int-7

[0131]

[0132] Under nitrogen protection, 20.0 mmol of Int-6 was dissolved in 50 mL of dry THF, cooled to 0 °C, and 22.0 mmol of 1 M methyl magnesium bromide THF solution was added dropwise. The mixture was then heated to room temperature and stirred for 1 hour. 50 mL of 2 M dilute hydrochloric acid aqueous solution was added, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The residue was purified by silica gel column chromatography to give intermediate Int-7, a white solid, in 92% yield.

[0133] Step 4: Preparation of intermediate Int-8

[0134]

[0135] Under nitrogen protection, 20.0 mmol of Int-7 was dissolved in 60 mL of dry dichloromethane, cooled to 0 °C, and 30.0 mmol of boron trifluoride diethyl ether solution was added dropwise. The mixture was stirred for 5 hours, and 50 mL of water was added. The organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The residue was purified by silica gel column chromatography to give intermediate Int-8, a white solid, in 84% yield.

[0136] Step 5: Preparation of compound D193

[0137]

[0138] Following the synthetic method in step 3 of Example 1, except that Int-2 was replaced with Int-8 in step 3 of Example 1, compound D193 was prepared as a yellow solid with a yield of 86%. 1HNMR (δ, CDCl3): 8.09~8.07(1H,m); 7.85~7.83(1H,m); 7.65~7.63(1H,m) ;7.62~7.59(4H,m);7.50~7.45(4H,m);7.40~7.33(3H,m);7.26~7.22(4H ,m); 7.09(1H,s); 7.06~7.02(4H,m); 2.80~2.64(2H,m); 2.39~2.34(1H,m ); 2.21~2.13(1H,m); 1.78~1.67(2H,m); 1.56~1.41(2H,m); 1.36(6H,s).

[0139] Compound D193 (X=O and X=S) was prepared according to the synthetic method of Example 1; X=O was a yellow solid, yield: 88%. 1 HNMR (δ, CDCl3): 8.25~8.23(1H,m); 8.09~8.07(1H,m); 7.62~7.59(4H,m); 7.51~7.45(5H,m); 7.40~7.33(3H,m); 7.26~7 .22(4H,m); 7.02(1H,s); 6.99~6.95(4H,m); 3.07~2.91(2H,m); 2.86~2.68(2H,m); 2.09~1.98(2H,m); 1.96~1.79(2H,m).

[0140] X = S, yellow solid, yield: 84%. 1 HNMR (δ, CDCl3): 8.38~8.36(1H,m); 8.10~8.08(1H,m); 7.62~7.59(4H,m); 7.51~7.45(5H,m); 7.40~7.33(3H,m) ); 7.26~7.22(4H,m); 7.04(1H,s); 7.01~6.97(4H,m); 3.59~3.36(4H,m); 2.04~1.86(2H,m); 1.80~1.62(2H,m).

[0141] Compound D193 (X = NPh) was prepared as a yellow solid with a yield of 86% by the synthetic method described in Example 2. 1HNMR (δ, CDCl3): 8.07~8.05(1H,m); 7.98~7.96(1H,m); 7.71~7.67(1H,m); 7.63~7.58(5H,m); 7.55~7.52(2H,m); 7.50~7.44(6H,m) ); 7.40~7.33(3H,m); 7.26~7.22(4H,m); 6.98(1H,s); 6.95~6.91(4H,m); 3.21~3.05(2H,m); 2.62~2.44(2H,m); 1.88~1.67(4H,m).

[0142] Examples 4 to 108

[0143] Following a similar synthetic method described above, the compounds shown in Table 1 were prepared:

[0144] Table 1

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155] In the above embodiments, *—X—* and *—T—* are each independently selected from *—O—*, *—S—*, or one of the structures shown below:

[0156]

[0157] *— and —* represent connector keys.

[0158] Example 109

[0159] An OLED element 100, such as Figure 1As shown, the OLED element in this embodiment is a top-emitting element, including 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 above the cathode. The method for fabricating an OLED element that does not include the hole blocking layer 107 includes the following steps:

[0160] 1) The glass substrate coated with the ITO conductive layer was ultrasonically treated in the cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in the acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with a UV cleaner for 10 minutes, and bombarded with a low-energy cation beam.

[0161] 2) Place the prepared ITO glass substrate into a vacuum chamber and evacuate to a vacuum level less than 1 × 10⁻⁶. -5 Pa, metallic silver is deposited as the anode layer on the above ITO film, and the thickness of the deposited film is [missing information]. Compounds HI01 and HI02 were then deposited separately as hole injection layers, with HI02 accounting for 3% of the mass of HI01, and the deposited film thickness was [missing information].

[0162] 3) Compound HTM01 is further deposited onto the aforementioned hole injection layer to form a hole transport layer, with a deposition thickness of [missing information].

[0163] 4) HTMO2 compound is further deposited as an electron blocking layer on the aforementioned hole transport layer, with a film thickness of [missing information].

[0164] 5) PH045 as the host material and BD045 as the dopant material are further deposited on the electron blocking layer, with BD045 accounting for 6% of the mass of PH045, to form the organic light-emitting layer of the device. The thickness of the resulting organic light-emitting layer is [missing information].

[0165] 6) A layer of LiQ and compound ET028 is deposited on the organic light-emitting layer as an electron transport layer for the device. The compound ET028 accounts for 50% of the mass of LiQ, and the deposited film thickness is [missing information].

[0166] 7) A LiF layer is deposited on top of the electron transport layer as an electron injection layer, with a deposition thickness of [missing information].

[0167] 8) A transparent cathode layer of magnesium and silver is deposited on top of the electron injection layer as the element, with a magnesium to silver mass ratio of 1:10, and the deposited film thickness is [missing information].

[0168] 9) A CPD layer is deposited on top of the transparent cathode layer as the light extraction layer for the device, with a deposition thickness of [missing information].

[0169] 10) A layer of the compound prepared in Examples 1 to 108 of this invention is deposited on top of the light extraction layer as a cover layer for the element, with a deposition film thickness of [missing information]. The OLED element provided by this invention is obtained.

[0170] The structure of the compound used in Example 109 above is as follows:

[0171]

[0172] Example 110

[0173] An organic electroluminescent element 200, the structure of which is as follows: Figure 2 As shown, it 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, a cathode 213, and a CPL, wherein the CPL includes the light extraction layer and the capping layer described in Example 109. The electroluminescent element 200 is fabricated using a similar method to Example 109.

[0174] Comparative Example 1

[0175] Following the same steps as in Example 109, the compound of the present invention in step 10) was replaced with B-4 to obtain Comparative element 1.

[0176] Comparative Example 2

[0177] Following the same steps as in Example 109, the compound of the present invention in step 10) was replaced with B-3 to obtain Comparative element 2.

[0178] The organic electroluminescent elements prepared by the above process were subjected to the following performance tests:

[0179] The driving voltage and current efficiency, as well as the lifetime of the organic electroluminescent elements prepared in Examples 109 and 110 and Comparative Examples 1 and 2, were measured using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1V per second, and the luminance of the organic electroluminescent element was measured when it reached 1000 cd / m². 2The voltage at that time is the driving voltage, and the current density at that time is measured simultaneously; the ratio of brightness to current density is the current efficiency; the LT90% lifespan test is as follows: using a luminance meter at 1000 cd / m² 2 At a constant current under the given brightness, the brightness decay of the organic electroluminescent element was measured to be 900 cd / m². 2 The time is in hours. The data listed in Table 2 are relative to Comparison Element 1.

[0180] Table 2

[0181]

[0182]

[0183]

[0184]

[0185] As shown in Table 2, the OLED devices prepared by the compounds of the present invention have a lower driving voltage than B-4 and B-3 at the same brightness, and the current efficiency is significantly improved, reaching up to 1.3 times that of the comparative devices. Moreover, the LT90% lifetime of the devices is greatly improved, indicating that the compounds of the present invention are high-performance capping layer materials.

[0186] The difference between compounds B-4 in Comparative Example 1 and B-3 in Comparative Example 2 and the compounds of the present invention lies in the fact that the parent nucleus groups of B-4 and B-3 in tetrahydrodibenzofuran have small planar surfaces, and the molecular twisting results in large steric hindrance. In contrast, the compounds of the present invention, after the introduction of tetrahydronaphthofuran, have larger planar surfaces of the parent nucleus groups, smaller steric sites, and lower refractive index, resulting in increased brightness under the same driving voltage. Therefore, under the same brightness conditions, the driving voltage is significantly reduced, power consumption is lowered, and the luminescent performance is superior, leading to a significant improvement in device performance.

[0187] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A cycloalkyl amino compound, characterized in that, The cycloalkyl amino compounds are selected from the group consisting of the following structures: 、 、 、 、 、 、 、 、 、 ； Wherein, n is 1; X is selected from O, S, CR 2 R 3 , or NAr 3 ; R 1 It is hydrogen; R 4 Choose from the group consisting of hydrogen, deuterium, fluorine, diphenylamino, and N-phenyl-1-naphthylamino. R 2 R 3 Each is independently selected from the group consisting of methyl, ethyl, phenyl, and fluorenyl groups; Ar 1 Ar 2 Ar 3 Each is independently selected from the group consisting of phenyl, diphenyl, triphenyl, tetraphenyl, naphthyl, phenanthrene, triphenylene, carbazolyl, fluorenyl, anthracene, fluoranyl, benzofuranyl, benzothiophene, dibenzofuranyl, or dibenzothiophene. The L 1 It is a single key.

2. A cycloalkyl amino compound, characterized in that, The cycloalkyl amino compounds are selected from the following compounds: Wherein, *—X—* and *—T—* are each independently selected from *—O—*, *—S—*, or one of the structures shown below: 、 、 、 、 、 、 、 、 、 ； *— and —* represent connector keys.

3. The use of the cycloalkyl amine compound of any one of claims 1-2 in the preparation of organic electroluminescent elements.

4. An organic electroluminescent element, characterized in that, It includes: 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 material of at least one of the organic layers or capping layers comprises a cycloalkyl amine compound as described in any one of claims 1-2.

5. The organic electroluminescent element according to claim 4, characterized in that, The organic layer includes 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; The hole injection layer or electron blocking layer comprises any one of the cycloalkyl amine compounds according to claims 1-2; And / or, the covering layer comprises a cycloalkyl amine compound as described in any one of claims 1-2.

6. A consumer electronic device, characterized in that, It includes the organic electroluminescent element as described in claim 4.

Images