CN113861040A - Organic compounds and their use in devices - Google Patents

Organic compounds and their use in devices Download PDF

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CN113861040A
CN113861040A CN202010621388.2A CN202010621388A CN113861040A CN 113861040 A CN113861040 A CN 113861040A CN 202010621388 A CN202010621388 A CN 202010621388A CN 113861040 A CN113861040 A CN 113861040A
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fused ring
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CN113861040B (en
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王志鹏
高文正
黄金华
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Beijing Eternal Material Technology Co Ltd
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Abstract

An organic compound having the structure of formula 1:
Figure DDA0002563136150000011
L1is a single bond, C2-C10 alkenylene, C6-C60 arylene or fused ring arylene, C3-C60 heteroarylene or fused ring heteroarylene; l is2Is arylene or fused ring arylene of C6-C60 or heteroarylene or fused ring heteroarylene of C3-C60; x is S, O, CR4R5、NR6Or SiR7R8；Ar1Is an aryl or fused ring aryl of C6-C60 or a heteroaryl or fused ring heteroaryl of C3-C60; r1‑R3Independently hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, C1-C30 linear or branched alkyl, C1-C30 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C60 aryl or fused ring aryl, or C3-C60 heteroaryl or fused ring heteroaryl, R1And R3Optionally fused to the attached aromatic ring; m, n, p are independently selected from the group consisting of integer values from 1 to the maximum, i.e., the upper limit of the respective substitutable positions; r4‑R8Each independently is C1-C30 alkyl, C1-C30 alkoxy, C6-C30 aryl, C3-C30 heteroaryl, R4And R5May be linked to each other to form a ring by a chemical bond.

Description

Organic compounds and their use in devices
Technical Field
The invention relates to the technical field of novel organic compounds and organic electroluminescence, in particular to a compound, application thereof and an organic electroluminescent device containing the compound.
Background
In recent years, optoelectronic devices based on organic materials have been rapidly developed and are the hot spot of research in the field. Examples of such organic optoelectronic devices include Organic Light Emitting Diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLEDs have been developed particularly rapidly, and have been commercially successful in the field of information display. The OLED can provide three colors of red, green and blue with high saturation, and a full-color display device manufactured by using the OLED does not need an additional backlight source and has the advantages of colorful, light, thin and soft color and the like.
The core of the OLED device is a multilayer thin film structure containing various organic functional materials. Common functionalized organic materials are: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like. When electricity is applied, electrons and holes are injected, transported to the light emitting region, and recombined therein, respectively, thereby generating excitons and emitting light.
Conventional fluorescent emitters emit light mainly by using singlet excitons generated when electrons and holes are combined, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can emit light using both triplet excitons and singlet excitons, which are called phosphorescent emitters, and the energy conversion efficiency can be increased by up to four times as compared with conventional fluorescent emitters. The thermal excitation delayed fluorescence (TADF) technology can still effectively utilize triplet excitons to achieve higher luminous efficiency without using a metal complex by promoting the conversion of triplet excitons to singlet excitons. Thermal excitation sensitized fluorescence (TASF) technology also achieves higher luminous efficiency by sensitizing the emitter by energy transfer using TADF-like materials.
The hole transport material has obvious influence on the voltage of the device, and on the other hand, the hole transport material also regulates and controls the transport balance of carriers in the device, improves the carrier mobility of the hole transport material, can improve the luminous efficiency and delay the attenuation of the device. Although the products adopting the OLED display technology are commercialized at present, the lifetime, efficiency, and other properties of the device are continuously improved to meet the pursuit of higher quality. Therefore, there is a need in the art to develop a wider variety of organic materials for organic electroluminescent devices, such that the devices have higher light emitting efficiency, lower driving voltage and longer service life.
Disclosure of Invention
Problems to be solved by the invention
In order to further meet the requirements of the OLED device for increasing its photoelectric properties and the requirements of the mobile electronic device for energy saving, it is necessary to develop a new and efficient OLED material, and it is important to develop a new hole transport material with high hole injection capability and high mobility.
The invention aims to provide a compound which can be used as an organic thin layer material in an organic electroluminescent device, so that the device has high luminous efficiency and long service life.
Means for solving the problemsScheme (2)
The inventor conducts intensive research and finds that a good hole transport layer material can be obtained by taking dinaphthylamine with excellent hole transport capacity as a parent nucleus, introducing a fused aromatic ring or fused heterocyclic ring structure with good conjugated planarity structure and thermal stability through other aromatic groups in a bridging manner, and introducing the aromatic groups at the ortho positions of anilino groups. The above materials of the present invention are also generally useful as electron blocking layer materials and perform equally well.
Specifically, one of the objects of the present invention is to provide an organic compound characterized by having a structure represented by formula 1:
Figure BDA0002563136140000021
wherein,
said L1Is a single bond, C2-C10 alkenylene, substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C9-C60 fused ring arylene, substituted or unsubstituted C3-C60 heteroarylene or substituted or unsubstituted C3-C60 fused ring heteroarylene;
said L2Is substituted or unsubstituted arylene of C6-C60, substituted or unsubstituted fused ring arylene of C9-C60, substituted or unsubstituted heteroarylene of C3-C60 or substituted or unsubstituted fused ring heteroarylene of C3-C60;
said X is S, O, CR4R5、NR6Or SiR7R8；
Ar is1Is substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C9-C60 fused ring aryl, substituted or unsubstituted C3-C60 heteroaryl or substituted or unsubstituted C3-C60 fused ring heteroaryl;
the R is1-R3Each independently is hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, C1-C30 linear or branched alkyl, C1-C30 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstitutedSubstituted C9-C60 fused ring aryl, substituted or unsubstituted C3-C60 heteroaryl or substituted or unsubstituted C3-C60 fused ring heteroaryl, R1And R3Optionally fused to the attached aromatic ring;
m, n, p are each independently selected from 1 to the maximum desirable integer value, i.e., the upper limit of the respective substitutable positions; when there are more than one R1、R2、R3When a plurality of R1、R2、R3Each may be the same or different (i.e., multiple R's)1Each being the same or different, a plurality of R2Each being the same or different, a plurality of R3Each the same or different);
the R is4-R8Each independently is C1-C30 alkyl, C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl, wherein R is4And R5May be linked to each other by a chemical bond to form a ring, R7And R8Can be connected with each other to form a ring through a chemical bond;
when the substituted or unsubstituted group has a substituent, the substituent is selected from one or a combination of at least two of deuterium, halogen, cyano, nitro, hydroxyl, carboxyl, aldehyde group, carbonyl, amino, C1-C30 linear or C1-C30 branched alkyl, C1-C30 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C60 aryl or C9-C60 fused ring aryl, C3-C60 heteroaryl or C3-C60 fused ring heteroaryl.
The compound of the invention takes dinaphthylamine with excellent hole transport capacity as a mother nucleus, introduces a fused aromatic ring or fused heterocyclic ring structure with good conjugated planarity structure and thermal stability through other aromatic groups in a bridging way, and introduces a specific aromatic group at the ortho position of an anilino group. The reason why it is excellent as a hole transport layer material or an electron blocking layer material in an organic electroluminescent device is not clear, and is presumed as follows.
In the compounds of the invention, dinaphthylamine as a parent nucleus has excellent hole transport capacity and can improve the charge mobility of a molecule; fused aromatic rings or fused heterocyclic structures such as 9, 9-dimethylfluorene, dibenzofuran, dibenzothiophene and the like introduced by other aromatic groups in a bridging manner have good conjugated planar structures and thermal stability, and the bridging of the fused aromatic rings or fused heterocyclic structures with the aromatic groups increases the conjugated capability of molecules and improves the transmission capability of cavities, so that the charge transmission and the molecular stability of the molecules are improved; on the other hand, the introduction of a group at the ortho position of the anilino improves the molecular triplet state energy level, and the high triplet state energy level can inhibit the loss of excitons in the light-emitting layer, prevent the excitons from transferring to the hole transport layer to cause charge imbalance in the light-emitting layer and prevent the efficiency roll-off of the device; meanwhile, because the ortho-position substitution has certain steric hindrance, the molecules can be prevented from being over-planarized to form crystals at high temperature. By such a combination of molecular structure design and groups, a device using the compound as a hole transport layer material or an electron blocking layer material can be ensured to achieve a low starting voltage, high device efficiency, and a long service life.
The inventors have found that if the fused aromatic ring or fused heterocyclic structure described above is directly attached to the nitrogen atom (i.e., L)2Single bond), the resulting material has reduced properties compared to the above-mentioned compounds of the invention, even if all other conditions are met. In other words, a fused aromatic ring or fused heterocyclic ring structure such as 9, 9-dimethylfluorene, dibenzofuran, dibenzothiophene, etc. must be bridged to the nitrogen atom of binaphthylamine by an aromatic group of a certain size, which may cause steric hindrance in addition to the increase of the conjugation ability of the fused aromatic ring or fused heterocyclic ring structure by the bridging with the aromatic group to improve the transport efficiency. Specifically, the benzene ring directly connected on N is connected with an aromatic group Ar with certain steric hindrance at the ortho position1If the fused aromatic or fused heterocyclic structure is directly attached to the nitrogen atom, it is reacted with Ar1The steric hindrance between them may be too great. Thus, L is satisfied at the same time2An aromatic subunit defined in the invention and Ar1Both conditions are necessary for the aromatic group defined for the present invention. The inventor combines the two together, and the compound molecule of the invention has excellent transmission efficiency and the steric hindrance is in a proper range based on the synergistic effect of the two. In this application, the termThe possible actions of the various groups/features are described separately for ease of illustration, but this does not mean that the groups/features act in isolation. In fact, the reason for obtaining good performance is essentially an optimized combination of the whole molecule, as a result of synergy between the individual groups, rather than the effect of a single group.
Specifically, L2Is substituted or unsubstituted arylene of C6-C60 or substituted or unsubstituted fused ring arylene of C9-C60, or substituted or unsubstituted heteroarylene of C3-C60 or substituted or unsubstituted fused ring heteroarylene of C3-C60, Ar1Is one or the combination of at least two of substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C9-C60 fused ring aryl, or substituted or unsubstituted C3-C60 heteroaryl or substituted or unsubstituted C3-C60 fused ring heteroaryl, and when the substituted or unsubstituted groups have substituents, the substituents are selected from deuterium, halogen, cyano, nitro, hydroxyl, carboxyl, aldehyde, carbonyl, amino, C1-C6 straight chain or C1-C6 branched alkyl, C1-C8 alkoxy, C3-C8 cycloalkyl, C3-C8 heterocycloalkyl, 6-C18 aryl or C9-C18 fused ring aryl, C3-C18 heteroaryl or C3-C18 fused ring heteroaryl.
L above2Preferred is a substituted or unsubstituted arylene group of C6 to C30 or a substituted or unsubstituted fused ring arylene group of C9 to C30, or a substituted or unsubstituted heteroarylene group of C3 to C30 or a substituted or unsubstituted fused ring heteroarylene group of C3 to C30, more preferred is a substituted or unsubstituted arylene group of C6 to C20 or a substituted or unsubstituted fused ring arylene group of C9 to C20, or a substituted or unsubstituted heteroarylene group of C3 to C20 or a substituted or unsubstituted fused ring heteroarylene group of C3 to C20, further preferred is phenylene, biphenylene, or naphthylene, and particularly preferred is phenylene.
Ar above1Preferably substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C9-C30 fused ring aryl, or substituted or unsubstituted C3-C30 heteroaryl or substituted or unsubstituted C3-C30 fused ring heteroaryl, more preferably substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C9-C20 fused ring aryl, or substituted or unsubstituted C9-C20 fused ring arylThe unsubstituted C3-C20 heteroaryl group or the substituted or unsubstituted C3-C20 fused ring heteroaryl group is more preferably a phenyl group or a biphenyl group, and particularly preferably a phenyl group.
By mixing L2And Ar1The steric hindrance of the molecules of the compound of the present invention can be more appropriately controlled by the above range, and the hole transport ability can be further improved, so that the molecular charge transport ability and the molecular stability can be improved, and the efficiency roll-off of the device can be prevented.
In the present invention, unless otherwise specified, a substituent is not condensed with a group in which it is present. For example, Ar mentioned above1、R2Are all connected to the parent nucleus by a single bond and are not fused to the parent nucleus. In addition, R1And R3Optionally fused to the aromatic ring to which it is attached, but preferably not fused to the aromatic ring to which it is attached.
The compounds of the present invention can also be represented by formula (1-1) and formula (1-2):
Figure BDA0002563136140000041
in the formulae (1-1) and (1-2), the same groups as described in the formula (1) are contained. The compound of the present invention preferably has a structure represented by the formula (1-1).
In the compounds of the present invention, L1Preferably a single bond; r1Preferably hydrogen or phenyl; r3Preferably hydrogen; r4-R8Each independently is preferably hydrogen, methyl, ethyl, phenyl or naphthyl.
In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, for example, hydrogen (H) includes1H (protium, or written as H),2H (deuterium, or denoted as D), etc.; carbon (C) then comprises12C、13C and the like.
In the compounds of the invention, R2Preferably hydrogen, C1-C20 linear or C1-C20 branched alkyl or phenyl, more preferably C1-C10 linear or C1-C10 branched alkyl, and still more preferably t-butyl. This is because of the alkyl groupHas good electron donating ability and can increase the blocking ability to excitons, so R2The compound of the present invention exhibits excellent properties when used in both a hole transport layer and an electron blocking layer when it is an alkyl group.
The alkyl group mentioned in the present invention includes a straight-chain alkyl group, a branched-chain alkyl group and a cyclic alkyl group, unless otherwise specified. Specifically, a substituted or unsubstituted C1-C30 alkyl group, preferably a C1-C16 alkyl group, more preferably a C1-C10 alkyl group. Examples of the C1-C10 alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like.
The substituted or unsubstituted aryl group having C6-C60 or the substituted or unsubstituted condensed ring aryl group having C9-C60 is preferably an aryl group having C6-C30 or a condensed ring aryl group having C9-C30, and more preferably a condensed ring aryl group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and derivatives thereof, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, etc,
Figure BDA0002563136140000051
A group of the group consisting of a phenyl group and a tetracenyl group. Specifically, the biphenyl group includes 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes a 1-naphthyl group or a 2-naphthyl group; the anthracene group is selected from 1-anthracene group, 2-anthracene group and 9-anthracene group; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the derivative group of the fluorene is selected from 9, 9-dimethylfluorenyl, 9-diethylfluorenyl, 9-dipropylfluorenyl, 9-dibutylfluorenyl, 9-diamylfluorenyl, 9-dihexylfluorenyl, 9-diphenylfluorenyl, 9-dinaphthylfluorenyl, spirofluorenyl and benzofluorenyl; the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracenyl is selected from the group consisting of 1-tetracenyl, 2-tetracenyl, and 9-tetracenyl.
The substituted or unsubstituted heteroaryl group of C3-C60 or substituted or unsubstituted heterocycle fused aryl group of C3-C60 is preferably heteroaryl group of C3-C30 or heterocycle fused aryl group of C3-C30, and more preferably is one or a combination of two or more groups selected from furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl, acridinyl, isobenzofuryl, isobenzothienyl, acridinyl, pyridyl, benzocarbazolyl, azacarbazolyl, phenothiazinyl, and phenazinyl.
Further, the compound of the general formula of the present invention is preferably the following specific compound, but the present invention is not limited to the specific compound shown below:
Figure BDA0002563136140000061
Figure BDA0002563136140000071
Figure BDA0002563136140000081
Figure BDA0002563136140000091
Figure BDA0002563136140000101
Figure BDA0002563136140000111
Figure BDA0002563136140000121
Figure BDA0002563136140000131
Figure BDA0002563136140000141
Figure BDA0002563136140000151
Figure BDA0002563136140000161
Figure BDA0002563136140000171
Figure BDA0002563136140000181
Figure BDA0002563136140000191
Figure BDA0002563136140000201
as another aspect of the present invention, there is also provided a use of the compound as described above in an organic electroluminescent device. In particular, it is preferable as a hole transport layer material or an electron blocking layer material in an organic electroluminescent device.
In addition to the organic electroluminescent device, the compound of the present invention can be applied to a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet type scanner, or electronic paper.
As still another aspect of the present invention, there is also provided an organic electroluminescent device comprising a first electrode, a second electrode and an organic layer interposed between the first electrode and the second electrode, characterized in that the organic layer contains the compound of formula (1) as described above or contains any of compounds C1 to C354 as described above.
Effects of the invention
The compound of the invention has excellent performance when used as a hole transport layer material or an electron blocking layer material in an organic electroluminescent device. Since the inventors have designed the kind of the group and steric hindrance thereof, it is possible to prevent the molecules from being excessively planarized to form crystals at high temperatures, and it is possible to ensure that a device using the compound as a hole transport layer material or an electron blocking layer material attains a low starting voltage, high device efficiency, and a long service life. Therefore, the OLED device prepared by the compound has excellent performance and can meet the requirements of panel manufacturing enterprises on high-performance materials at present.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the present invention, a method for synthesizing the above compounds is briefly described, and a representative synthetic route of the compound of formula 1 is as follows:
Figure BDA0002563136140000211
the solvents and reagents used in the following synthesis examples of the present invention, such as toluene and methanol, can be purchased or customized from domestic chemical product markets, such as reagents from national drug group, Sigma-Aldrich, and Bailingwei, and the intermediates (such as M1) involved in the experiment can be customized by the reagents. In addition, they can be synthesized by a known method by those skilled in the art.
The mass spectrum characterization data in the following synthesis examples were obtained by a ZAB-HS type mass spectrometer test manufactured by Micromass, UK.
Synthesis example 1: synthesis of Compound C1
Figure BDA0002563136140000221
In a 250mL single-necked flask, 15.0g (55.8mmol) of M1, 12.9g (55.8mmol) of o-bromobiphenyl, 0.5g (0.56mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)2(dba)3) 0.46g (1.12mmol) of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (namely SPhOS), 250mL of Toluene (Toluene) and 7.0g (72.5mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and heating the reaction to 80 ℃ for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction solution, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder CM 1.
In a 250mL single-neck flask, 10g (23.8mmol) of CM1, 8.0g (25.0mmol) of 2- (4-bromophenyl) dibenzofuran, 0.18g (0.2mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)2(dba)3) 0.3mL of tritertine butylphosphine ((t-Bu)3P), 150mL of Toluene (Toluene), 3.0g (30.9mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and heating the reaction to 100 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder C1, wherein the theoretical value of M/Z is as follows: 662, measured value of M/Z: 663(M + H).
The compounds in table 1 below were obtained according to the method for the synthesis of compound C1, replacing the corresponding starting materials:
table 1: synthesis of example Compounds
Figure BDA0002563136140000222
Figure BDA0002563136140000231
Figure BDA0002563136140000241
Figure BDA0002563136140000251
Device embodiments
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used2) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multi-layer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL); wherein the HIL is located between the anode and the HTL and the EBL is located between the HTL and the light emitting layer.
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derived groups such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derived groups such as compounds shown below in HT-1 to HT-30; or any combination thereof.
Figure BDA0002563136140000261
Figure BDA0002563136140000271
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-30 described above, or one or more compounds of HI-1-HI-3 described below; one or more of the compounds HT-1 to HT-30 may also be used to dope one or more of the compounds HI-1-HI-3 described below.
Figure BDA0002563136140000281
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light-emitting layer is selected from, but not limited to, one or more of PH-1 to PH-85.
Figure BDA0002563136140000282
Figure BDA0002563136140000291
Figure BDA0002563136140000301
Figure BDA0002563136140000311
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer can be selected from, but is not limited to, one or more of GPD-1 to GPD-47 listed below.
Figure BDA0002563136140000321
Figure BDA0002563136140000331
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.
Figure BDA0002563136140000332
Figure BDA0002563136140000341
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light-emitting layer can be selected from, but is not limited to, one or more of YPD-1-YPD-11 listed below.
Figure BDA0002563136140000342
In one aspect of the invention, an Electron Blocking Layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but is not limited to, one or more compounds of HT-1 to HT-30, as described above, or one or more compounds of PH-47 to PH-77, as described above; mixtures of one or more compounds from HT-1 to HT-30 and one or more compounds from PH-47 to PH-77 may also be used, but are not limited thereto.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-65 listed below.
Figure BDA0002563136140000351
Figure BDA0002563136140000361
Figure BDA0002563136140000371
In one aspect of the invention, a Hole Blocking Layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more compounds from ET-1 to ET-65 or one or more compounds from PH-1 to PH-46; mixtures of one or more compounds from ET-1 to ET-65 with one or more compounds from PH-1 to PH-46 may also be used, but are not limited thereto.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following.
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca，Mg。
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to<1×10-5Pa, vacuum thermal evaporation of 10nm HT-4: HI-3(97/3, w/w) mixture as hole injection layer on the anode layer film in sequence, 60nm compound HT-4 as hole transport layer, 5nm of compound HT-14 as electron blocking layer; a binary mixture of a compound PH-34 of 40nm and RPD-10(100:3, w/w) is used as a light-emitting layer; 5nm of ET-23 as a hole blocking layer, 25nm of a mixture of compounds ET-61: ET-57(50/50, w/w) as an electron transport layer, 1nm of LiF as an electron injection layer, and 150nm of metallic aluminum as a cathode. The total evaporation rate of all the organic layers and LiF is controlled at 0.1 nm/s, and the evaporation rate of the metal electrode is controlled at 1 nm/s.
Examples 1 to 9 where the compounds of the present invention were used as hole transport materials, the HT-4 compounds in the above preparation process were replaced with the compounds of the present invention as listed in Table 2; comparative examples 1-2 the HT-4 compound was replaced with R-1 and R-3.
Examples 10-17 replace the HT-14 compound in the above preparation process with the compounds of the present invention listed in table 3 when the compounds of the present invention are used as electron blocking materials; comparative examples 3-6 HT-14 compounds were replaced with R-1, R-2, R-4, R-5.
The above comparative example compounds R-1 to R-5 are as follows:
Figure BDA0002563136140000381
the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 14 and comparative examples 1 to 5 and the lifetime of the devices were measured at the same luminance using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 3000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT97 is as follows: using a luminance meter at 10000cd/m2The luminance drop of the organic electroluminescent device was measured to be 9700cd/m with a constant current maintained at luminance2Time in hours.
Table 2: the performance of the device prepared by the compound of the invention is compared with that of the device prepared by the compound of the prior art when the compound is used as a hole transport material
Device example numbering Hole transport layer material Electron barrier material Efficiency (cd/A) Life (h)
Comparative example 1 R-1 HT-14 16.5 60
Comparative example 2 R-3 HT-14 15.8 52
Example 1 C1 HT-14 17.5 83
Example 2 C121 HT-14 17.8 86
Example 3 C123 HT-14 17.0 75
Example 4 C205 HT-14 18.1 95
Example 5 C319 HT-14 18.5 103
Example 6 C301 HT-14 18.2 100
Example 7 C61 HT-14 17.2 80
Example 8 C284 HT-14 17.6 90
Example 9 C348 HT-14 17.4 88
From the results in table 2, it can be seen that when the compound of the present invention is used as a hole transport material for a device, the current efficiency can be 17.0cd/a or more, and the lifetime is greatly improved, and the compound is a hole transport material with good performance.
The compound R-1 in comparative example 1 is different from the compound C205 in example 4 only in that the dibenzo five-membered ring group in R-1 is 9, 9-dimethylfluorene, which is directly linked to N, while the dibenzofuran in C205 is linked to N through a phenylene group. From the performance data, C205 is superior to R-1. This is because dibenzofuranylphenyl has a longer conjugated structure than fluorenyl, and the bridging group also adjusts steric hindrance to a suitable range, which is beneficial to improving hole mobility, making charge transport of the device more balanced, and thus achieving higher efficiency and lifetime.
Similarly, the compound R-3 in comparative example 2 is different from C121 in example 2 mainly in that R-3 is 9, 9-dimethylfluorene at the 2-position, and in C121, a fluorene group is linked by bridging a benzene ring. From the performance data, the C121 efficiency is 17.8cd/A, and the service life is 86 hours, which are all superior to that of the comparative example 2. This is because the longer conjugated structure improves the hole transport ability of the molecule, while the bridging group also adjusts the steric hindrance to a suitable range, thereby improving device performance.
Table 3: the performance of the device prepared by the compound of the invention is compared with that of the device prepared by the compound of the prior art when the compound is used as an electron blocking material
Figure BDA0002563136140000391
Figure BDA0002563136140000401
The structural difference between the compound R-2 used in comparative example 4 and the compound C123 used in example 12 is that R-2 is substituted by p-biphenyl and C123 is substituted by o-biphenyl, and the device results show that the device efficiency is 17.8cd/A and the lifetime is 80 hours, which are superior to those of comparative example 4 when C123 is used as the electron blocking layer. The reason is that the ortho-position substituent group has certain steric hindrance, so that the triplet state energy level of the molecule is improved, the exciton generated in the luminescent layer can be prevented from transferring to the hole transport layer, the utilization rate of the exciton is improved, the efficiency is improved, and the service life is prolonged.
R-4 used in comparative example 5 is naphthyl and C4 is ortho-substituted biphenyl, as compared to C4 in example 11. Although naphthyl has better planarity and is beneficial to hole transmission, due to the lack of steric hindrance of ortho-position substituent groups, the triplet state energy level of molecules is influenced, the blocking capability to excitons is poor, and the efficiency is lower and is 14.8 cd/A.
The compound of the invention takes dinaphthylamine with excellent hole transport capacity as a mother nucleus, introduces a fused aromatic ring or fused heterocyclic ring structure with good conjugated planarity structure and thermal stability through other aromatic groups in a bridging way, and introduces a specific aromatic group at the ortho position of an anilino group. In contrast, in R-5 used in comparative example 6, the parent nucleus is not binaphthylamine but naphthylphenanthreneamine, so that the technical effects of the present invention cannot be achieved, and the performance of the organic electroluminescent device prepared therefrom is lower than that of the examples of the present invention.
On the other hand, we can note that when the compound of the present invention contains alkyl substitution, it exhibits excellent performance in both the hole transport layer and the electron blocking layer. The device efficiencies of C301 in example 6, C319 in example 5 and C301 in example 15 in the case of hole transport materials and electron blocking materials are all above 18 cd/A. This shows that when the compound Ar of the present invention is used as the compound1With alkyl substitution on the attached phenyl ring (i.e. R)2Is alkyl), can be obtainedThe reason why the device performance is more excellent is that the alkyl group has good electron donating capability and can increase the blocking capability of excitons, and the two reasons are that the material shows more excellent performance.
The above results show that the novel organic materials of the present invention can produce more excellent properties through specific structural combinations. When the material is used for an organic electroluminescent device, the current efficiency can be effectively improved, the service life of the device is prolonged, and the material is a hole transport material and an electron blocking material with good performance.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.

Claims (11)

1. An organic compound having a structure according to formula 1:
Figure FDA0002563136130000011
wherein,
said L1Is a single bond, C2-C10 alkenylene, substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C9-C60 fused ring arylene, substituted or unsubstituted C3-C60 heteroarylene or substituted or unsubstituted C3-C60 fused ring heteroarylene;
said L2Is substituted or unsubstituted arylene of C6-C60, substituted or unsubstituted fused ring arylene of C9-C60, substituted or unsubstituted heteroarylene of C3-C60 or substituted or unsubstituted fused ring heteroarylene of C3-C60;
said X is S, O, CR4R5、NR6Or SiR7R8；
Ar is1Is substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted condensed ring aryl of C9-C60, substituted or unsubstituted heteroaryl of C3-C60 or substituted or unsubstitutedUnsubstituted C3-C60 fused ring heteroaryl;
the R is1-R3Each independently is hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, C1-C30 linear or branched alkyl, C1-C30 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C9-C60 fused ring aryl, substituted or unsubstituted C3-C60 heteroaryl or substituted or unsubstituted C3-C60 fused ring heteroaryl, R is1And R3Optionally fused to the attached aromatic ring;
m, n, p are each independently selected from 1 to the maximum desirable integer value, i.e., the upper limit of the respective substitutable positions; when there are more than one R1、R2、R3When a plurality of R1、R2、R3Each may be the same or different;
the R is4-R8Each independently is C1-C30 alkyl, C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl, wherein R is4And R5May be linked to each other by a chemical bond to form a ring, R7And R8Can be connected with each other to form a ring through a chemical bond;
when the substituted or unsubstituted group has a substituent, the substituent is selected from one or a combination of at least two of deuterium, halogen, cyano, nitro, hydroxyl, carboxyl, aldehyde group, carbonyl, amino, C1-C30 linear or branched alkyl, C1-C30 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C60 aryl or C9-C60 fused ring aryl, C3-C60 heteroaryl or C3-C60 fused ring heteroaryl.
2. The organic compound of claim 1, having a structure according to formula 1-1:
Figure FDA0002563136130000021
in the formula 1-1, the L1、L2、Ar1、R1-R3X, m, n, p all have the same limitations as in formula 1.
3. The organic compound of claim 1, wherein L is1Is a single bond.
4. The organic compound of claim 1, wherein L is2Is substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted fused ring arylene of C9-C30, substituted or unsubstituted heteroarylene of C3-C30 or substituted or unsubstituted fused ring heteroarylene of C3-C30, preferably L2Is phenylene, biphenylene or naphthylene, more preferably L2Is phenylene.
5. The organic compound of claim 1, wherein Ar is Ar1Is substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C9-C30 fused ring aryl, substituted or unsubstituted C3-C30 heteroaryl or substituted or unsubstituted C3-C30 fused ring heteroaryl, preferably Ar1Is phenyl or biphenyl, more preferably Ar1Is phenyl.
6. The organic compound of claim 1, wherein R is1Is hydrogen or phenyl, said R3Is hydrogen.
7. The organic compound of claim 1, wherein R is2Is hydrogen, a linear or branched alkyl group of C1-C20 or phenyl, preferably R2Is a linear or branched alkyl group of C1-C10, more preferably R2Is a tert-butyl group.
8. The organic compound of claim 1, wherein R is4-R8Each independently hydrogen, methyl, ethyl, phenyl or naphthyl.
9. The organic compound according to claim 1, wherein the organic compound has a structure represented by C1 to C354:
Figure FDA0002563136130000031
Figure FDA0002563136130000041
Figure FDA0002563136130000051
Figure FDA0002563136130000061
Figure FDA0002563136130000071
Figure FDA0002563136130000081
Figure FDA0002563136130000091
Figure FDA0002563136130000101
Figure FDA0002563136130000111
Figure FDA0002563136130000121
Figure FDA0002563136130000131
Figure FDA0002563136130000141
Figure FDA0002563136130000151
Figure FDA0002563136130000161
Figure FDA0002563136130000171
。
10. use of the organic compound according to any one of claims 1 to 9 in an organic electroluminescent device, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet type scanner, or an electronic paper, preferably as a hole transport layer material or an electron blocking layer material in an organic electroluminescent device.
11. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer interposed between the first electrode and the second electrode, characterized in that the organic layer contains at least one organic compound according to any one of claims 1 to 9.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057718A (en) * 2022-01-17 2022-02-18 浙江华显光电科技有限公司 Triphenylamine derivative, preparation, organic photoelectric device and display or lighting device
WO2023026864A1 (en) * 2021-08-26 2023-03-02 出光興産株式会社 Compound, organic electroluminescent element material, organic electroluminescent element, and electronic device
US12010910B2 (en) * 2021-04-21 2024-06-11 Shaanxi Lighte Optoelectronics Material Co., Ltd. Nitrogen-containing compound, and electronic element and electronic device comprising same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110511151A (en) * 2019-04-30 2019-11-29 北京鼎材科技有限公司 A kind of compound, the organic electroluminescence device comprising it and its application
CN111201625A (en) * 2018-01-08 2020-05-26 株式会社Lg化学 Organic light emitting device
CN111247652A (en) * 2018-02-23 2020-06-05 株式会社Lg化学 Organic light emitting device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111201625A (en) * 2018-01-08 2020-05-26 株式会社Lg化学 Organic light emitting device
CN111247652A (en) * 2018-02-23 2020-06-05 株式会社Lg化学 Organic light emitting device
CN110511151A (en) * 2019-04-30 2019-11-29 北京鼎材科技有限公司 A kind of compound, the organic electroluminescence device comprising it and its application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12010910B2 (en) * 2021-04-21 2024-06-11 Shaanxi Lighte Optoelectronics Material Co., Ltd. Nitrogen-containing compound, and electronic element and electronic device comprising same
WO2023026864A1 (en) * 2021-08-26 2023-03-02 出光興産株式会社 Compound, organic electroluminescent element material, organic electroluminescent element, and electronic device
CN114057718A (en) * 2022-01-17 2022-02-18 浙江华显光电科技有限公司 Triphenylamine derivative, preparation, organic photoelectric device and display or lighting device

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