CN112864334A - Organic electroluminescent device containing light extraction layer material - Google Patents

Organic electroluminescent device containing light extraction layer material Download PDF

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CN112864334A
CN112864334A CN202010745953.6A CN202010745953A CN112864334A CN 112864334 A CN112864334 A CN 112864334A CN 202010745953 A CN202010745953 A CN 202010745953A CN 112864334 A CN112864334 A CN 112864334A
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CN112864334B (en
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李涛
龙芷君
杨曦
宋晶尧
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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Abstract

In order to improve device performance, particularly light extraction efficiency, of an organic electroluminescent device, the present invention provides an organic electroluminescent device comprising a light extraction layer, wherein the light extraction layer material is selected from triarylamine compounds containing triphenylene and an electron-withdrawing group. The light extraction material provided by the invention has a higher extinction coefficient in an ultraviolet region and a higher refractive index in a visible light region, can reduce the damage of external high-energy light to the internal material of the organic electroluminescent display device, and improves the light extraction rate and the luminous efficiency of the device.

Description

Organic electroluminescent device containing light extraction layer material
The present application claims priority from the chinese patent application entitled "an organic electroluminescent device comprising a light extraction layer material" filed by the chinese patent office on 12/11/2019 under the application number 201911098682.3, the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent device containing a light extraction layer material. The invention further relates to an organic compound and application thereof in an organic electroluminescent device.
Background
Organic electroluminescent display devices are self-luminous display devices that generate excitons by transfer and recombination of carriers between functional layers and emit light by means of organic compounds or metal complexes having high quantum efficiency. The LED lamp has the characteristics of self-luminescence, high brightness, high efficiency, high contrast, high responsiveness and the like.
In recent years, the luminous efficiency of organic electroluminescent diodes (OLEDs) has been greatly improved, but the internal quantum efficiency thereof has approached the theoretical limit. Therefore, improvement of light extraction efficiency is an effective means for further improving device stability and current efficiency (e.g., deposition of metal complexes in the emission layer, matching of refractive indices between functional layers, etc.).
In such a light emitting device, when light emitted from a light emitting layer enters another functional layer, if the light enters at a certain angle or more, total reflection occurs between the light emitting layer and the other functional layer. Thus, only a portion of the emitted light can be utilized. In recent years, in order to improve light extraction efficiency, it has been proposed to provide a light extraction layer on the outside of a translucent electrode having a low refractive index. In 2001, Hung et al covered the surface of a metal cathode with a layer of about 50nm of organic or inorganic compound to improve the performance of the device by controlling the thickness and refractive index. In 2003, Riel et al have attempted to evaporate ZnSe, an inorganic compound having a high refractive index (n ═ 2.6), on a cathode, and improve light extraction efficiency by using the difference in refractive index between functional layers, but such compounds have not been much used in organic electroluminescent devices due to the high evaporation temperature and slow evaporation rate of inorganic materials.
Therefore, a new class of materials for improving light extraction efficiency of organic electroluminescent devices needs to be further developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, it is a primary object of the present invention to provide an organic electroluminescent device including a light extraction layer for improving the light extraction efficiency of the device. The invention further provides a novel organic compound and application thereof in an organic electroluminescent device.
In view of the above, it is possible to attempt to use an organic compound having a higher refractive index in an electroluminescent device to improve light extraction efficiency. Such compounds need to satisfy the following conditions: the extinction coefficient is high in an ultraviolet band (less than 400nm), and adverse effects of harmful light on device materials are avoided; the extinction coefficient is close to 0 in the visible light range (>430nm), the visible light has higher transmittance, and the influence on the light extraction efficiency of the equipment is reduced; the high-refractive-index optical material has high refractive index and small difference in a visible light range, and has the characteristics of improving light output and optimizing device structures and the like; has higher glass transition temperature and improves the thermal stability of the compound.
The technical scheme of the invention is as follows:
an organic electroluminescent device comprising two electrodes, one or more organic functional layers disposed between the two electrodes, and a light extraction layer disposed on a surface of one of the electrodes on a side away from the organic functional layer, the light extraction layer material comprising a compound represented by general formula (1):
Figure BDA0002608371730000011
wherein:
L1、L2and L3Each independently selected from a single bond, a substituted or unsubstituted aromatic or heteroaromatic group of 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system of 3 to 30 ring atoms;
Ar1selected from electron withdrawing groups; ar (Ar)2Selected from substituted or unsubstituted condensed ring aromatic group or condensed ring hetero aromatic group with 10-30 ring atoms;
v is independently selected from CR at each occurrence1Or N;
R1each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silylA keto group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, a CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
The invention further relates to an organic compound selected from the structures represented by the general formula (4):
Figure BDA0002608371730000021
wherein:
L1and L3Each independently selected from a single bond, a substituted or unsubstituted aromatic or heteroaromatic group of 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system of 3 to 30 ring atoms;
L2selected from a single bond or any of the following groups:
Figure BDA0002608371730000022
W、W1each occurrence is independently selected from CR9Or N;
Y2、Y3each occurrence is independently selected from NR10、CR10R11、O、S、SiR10R11、S＝O、SO2Or PR10；
R9、R10And R11Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched-chain or branched-chain alkyl having 3 to 20C atomsCyclic alkyl, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
The invention relates to a composition comprising at least one organic compound as described above, and at least one organic solvent.
The invention relates to a light extraction layer material comprising the organic compound.
Has the advantages that:
the light extraction layer material has higher glass transition temperature, higher thermal stability of the compound, high extinction coefficient in ultraviolet band, smaller extinction coefficient in visible light range and higher refractive index. When used in an organic electroluminescent device, it is possible to avoid adverse effects of harmful light on the internal material of the device and to improve the visible light extraction efficiency.
Drawings
FIG. 1 is a schematic diagram of a device embodiment. Fig. 1 is a structural view of a light emitting device according to an embodiment of the present invention, in which 1 is a substrate, 2 is an anode, 3a is a Hole Injection Layer (HIL), 3b is a Hole Transport Layer (HTL), 3c is a light emitting layer, 3d is an Electron Transport Layer (ETL), 3e is an Electron Injection Layer (EIL), 4 is a cathode, and 5 is a light extraction layer;
FIG. 2 is a UV-VIS absorption spectrum of compound C2 in dichloromethane;
FIG. 3 is a mass spectrum of compound C2.
Detailed Description
The present invention provides an organic electroluminescent device comprising a triarylamine compound of triphenylene as a material of a light extraction layer. The invention also relates to an organic compound containing triphenylene. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with art-acceptable groups including, but not limited to: c1-30An alkyl group, a cycloalkyl group having 3 to 20 ring atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 5 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted by a substituent acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c1-6Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, "adjacent groups" means that these groups are bonded to the same carbon atom or bonded to adjacent carbon atoms. These definitions apply correspondingly to "adjacent substituents".
An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group that contains at least one heteroatom. Further, the heteroatom is selected from Si, N, P, O, S and/or Ge, further from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are likewise considered aromatic or heterocyclic aromatic groups for the purposes of the present invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, further less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered fused aromatic ring systems for the purposes of the present invention.
In a certain preferred embodiment, the fused ring aromatic group is selected from: naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the fused ring heteroaromatic group is selected from the group consisting of benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.
In the present invention, the "light extraction layer" is a layer located on the electrode surface of the organic electroluminescent device and on the side away from the organic functional layer.
An organic electroluminescent device comprising two electrodes, one or more organic functional layers disposed between the two electrodes, and a light extraction layer disposed on a surface of one of the electrodes on a side away from the organic functional layer, the light extraction layer material comprising a compound represented by general formula (1):
Figure BDA0002608371730000031
wherein:
L1、L2and L3Each independently selected from a single bond, a substituted or unsubstituted aromatic or heteroaromatic group of 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system of 3 to 30 ring atoms;
Ar1selected from electron withdrawing groups; ar (Ar)2Selected from substituted or unsubstituted condensed ring aromatic group or condensed ring hetero aromatic group with 10-30 ring atoms; the molar refraction of condensed rings is higher, so that the refractive index of the molecules can be effectively improved;
v is independently selected from CR at each occurrence1Or N; preferably, V is independently selected for each occurrence from CR1；
R1Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atomsCyclic alkoxy, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF, hydroxyl, or a salt thereof3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
In one embodiment, Ar2Selected from substituted or unsubstituted condensed ring aromatic groups or condensed ring heteroaromatic groups with 14-30 ring atoms; in one embodiment, Ar2Selected from substituted or unsubstituted condensed ring aromatic groups with 14-30 ring atoms;
in one embodiment, Ar2Any one group selected from (A-1) to (A-5):
Figure BDA0002608371730000041
wherein:
x is independently selected from CR at each occurrence2Or N; when X and L are2When linked, X is selected from C; preferably, X is selected from CR at each occurrence2；
R2Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, sulfurCyanate, isothiocyanate, hydroxy, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
Further, Ar2Selected from (A-1), (A-2) or (A-4); further, Ar2Is selected from (A-1).
In one embodiment, Ar2Selected from any one of the following groups, wherein the H atoms on the ring may be further substituted:
Figure BDA0002608371730000042
further, Ar2Is selected from
Figure BDA0002608371730000043
Further, Ar2Is selected from
Figure BDA0002608371730000044
Further, Ar2Is selected from
Figure BDA0002608371730000045
In one embodiment, formula (1) is selected from any one of formulae (2-1) to (2-4):
Figure BDA0002608371730000046
wherein: x, V, L1、L2And L3、Ar1The meaning is the same as above.
In one embodiment, V in each of the general formulas (2-1) - (2-4) is selected from CR1(ii) a Further, R1Is selected from H; in one embodiment, X in each of the general formulas (2-1) - (2-4) is selected from CR2(ii) a Further, the method can be used for preparing a novel material，R2Is selected from H; in one embodiment, V in each of the general formulas (2-1) - (2-4) is selected from CR1X is selected from CR2。
In one embodiment, formulae (2-1) - (2-4) are selected from the following formulae:
Figure BDA0002608371730000051
in one embodiment, Ar1Selected from electron withdrawing groups; the reason is that the electron push-pull of the whole molecule can be improved, the energy level and dipole moment of the molecule can be regulated, and the ultraviolet absorption of the molecule under the wavelength of 400nm and the refractive index of the molecule can be improved.
Further, Ar1Selected from any one of the following groups:
Figure BDA0002608371730000052
wherein:
X1each occurrence is independently selected from CR3Or N, and at least one X1Is selected from N; in one embodiment, at least 2X1Is selected from N;
each occurrence of Y is independently selected from NR4、CR4R5、O、S、SiR4R5、S＝O、SO2Or PR4；
R3、R4And R5Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanateAcid ester, hydroxy, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
Further, Ar1Is selected from
Figure BDA0002608371730000053
Further, Ar1Is selected from
Figure BDA0002608371730000054
In a preferred embodiment, Ar1Selected from any one of the following groups, the dotted line representing the attachment site:
Figure BDA0002608371730000055
in a preferred embodiment, Ar1Selected from any one of the following groups:
Figure BDA0002608371730000061
wherein: the H atoms on the ring may be further substituted.
More preferably, Ar1Selected from any one of the following groups, the H atom on the ring may be further substituted, the dotted line representing the attachment site:
Figure BDA0002608371730000062
in one embodiment, formula (1) is selected from formula (3-1) or (3-2):
Figure BDA0002608371730000063
in one embodiment, V in formula (3-1) or (3-2) is selected from CR1(ii) a Further, R1Is selected from H; in one embodiment, X in formula (3-1) or (3-2) is selected from CR2(ii) a Further, R2Is selected from H; in one embodiment, V in formula (3-1) or (3-2) is selected from CR1X is selected from CR2。
In one embodiment, formula (3-1) or (3-2) is selected from the following formulas:
Figure BDA0002608371730000064
wherein: the H atoms on the ring may be further substituted.
In one embodiment, formula (3-1) is selected from the following formulas:
Figure BDA0002608371730000071
wherein: v, X1，R3，R4，L1，L2，L3The definition is the same as above.
In one embodiment, L1、L2And L3Each independently selected from a single bond or any of the following groups:
Figure BDA0002608371730000072
wherein:
X2each occurrence is independently selected from CR6Or N;
Y1each occurrence is independently selected from NR7、CR7R8、O、S、SiR7R8、S＝O、SO2Or PR7；
R6、R7And R8Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, having 1 to 20Linear thioalkoxy of 20C atoms, branched or cyclic alkyl of 3 to 20C atoms, branched or cyclic alkoxy of 3 to 20C atoms, branched or cyclic thioalkoxy of 3 to 20C atoms, silyl, keto of 1 to 20C atoms, alkoxycarbonyl of 2 to 20C atoms, aryloxycarbonyl of 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thioisocyanate, isothiocyanate, hydroxy, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
In one embodiment, L1、L2And L3At least one of them is selected from single bonds; in one embodiment, L1、L2And L3At least two of which are selected from single bonds; in one embodiment, L1、L2And L3Are all selected from single bonds.
In one embodiment, L1、L2And L3At least one selected from
Figure BDA0002608371730000073
In one embodiment, L1、L2And L3At least two of
Figure BDA0002608371730000074
In one embodiment, L1、L2And L3Are all selected from
Figure BDA0002608371730000075
In one embodiment, L1、L2And L3At least one selected from
Figure BDA0002608371730000076
In one embodiment, L1、L2And L3At least two of which are selected from
Figure BDA0002608371730000077
In one embodiment, L1、L2And L3Are all selected from
Figure BDA0002608371730000078
In one embodiment, L1、L2And L3Are all selected from single bonds or
Figure BDA0002608371730000079
In one embodiment, L1、L2And L3At least one is selected from single bonds and at least one is selected from
Figure BDA0002608371730000081
In one embodiment, L1、L2And L3One is selected from single bonds and two are selected from
Figure BDA0002608371730000082
In one embodiment, L1、L2And L3Two of them are selected from single bonds and one is selected from
Figure BDA0002608371730000083
In one embodiment, X is as defined above2Selected from the group consisting of CR6(ii) a Further, R6Is selected from H.
In one embodiment, L1、L2And L3Each independently selected from any one of the following groups:
Figure BDA0002608371730000084
wherein: the H atoms on the ring may be further substituted.
In particular, L1、L2And L3Are each independently selected fromA single bond or any of the following groups, the dotted line representing the attachment site:
Figure BDA0002608371730000085
wherein: the H atoms on the ring may be further substituted.
Specifically, the organic electroluminescent device according to the present invention, wherein the light extraction layer material is selected from the following structures but not limited thereto:
Figure BDA0002608371730000086
Figure BDA0002608371730000091
Figure BDA0002608371730000101
Figure BDA0002608371730000111
Figure BDA0002608371730000121
Figure BDA0002608371730000131
Figure BDA0002608371730000141
wherein: h in the above structure may be further optionally substituted.
According to the organic electroluminescent device, the material of the light extraction layer needs higher glass transition temperature, and the thermal stability of the material of the light extraction layer is improved. In certain preferred embodiments, the glass transition temperature Tg is 100 deg.C or higher, in a preferred embodiment 120 deg.C or higher, in a more preferred embodiment 140 deg.C or higher, in a more preferred embodiment 160 deg.C or higher, and in a most preferred embodiment 180 deg.C or higher.
In some embodiments, according to the organic electroluminescent device of the present invention, the refractive index of the light extraction layer material at a wavelength of 630nm is greater than 1.7; preferably, greater than 1.78; more preferably, greater than 1.83.
In other embodiments, according to the organic electroluminescent device of the present invention, the singlet energy (S1) of the material of the light extraction layer is greater than or equal to 2.7 eV; preferably, greater than or equal to 2.8 eV; more preferably, greater than or equal to 2.85 eV.
In other embodiments, according to the organic electroluminescent device of the present invention, the singlet energy (S1) of the material of the light extraction layer is less than or equal to 3.1 eV; preferably, less than or equal to 3.0 eV;
according to the organic electroluminescent device, the material of the light extraction layer needs a smaller extinction coefficient, and the extinction coefficient is less than 0.1 when the wavelength is 430 nm; preferably, less than 0.003; more preferably, less than 0.001. The light-emitting diode has higher transmittance on visible light, and the influence on the light-emitting efficiency of equipment is reduced.
In certain preferred embodiments, the organic electroluminescent device according to the invention has a light extraction layer with a large extinction coefficient in the wavelength range of 400nm or less; preferentially, the extinction coefficient is more than or equal to 0.3 when the wavelength is 350 nm; it is preferably not less than 0.5, more preferably not less than 0.7, most preferably not less than 1.0.
In a preferred embodiment, the organic electroluminescent device according to the present invention comprises one or more organic functional layers selected from one or more of an electron injection layer, an electron transport layer, a hole blocking layer, a hole injection layer, a hole transport layer, an electron blocking layer and a light emitting layer, including at least one light emitting layer.
In certain preferred embodiments, the organic electroluminescent device according to the present invention, wherein the organic functional layer is selected from a hole transport layer, a light emitting layer and an electron transport layer.
In certain more preferred embodiments, the organic electroluminescent device according to the present invention, wherein the organic functional layer is selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
In certain preferred embodiments, the organic electroluminescent device according to the present invention, wherein the light-emitting material in the light-emitting layer is selected from singlet emitters, triplet emitters or TADF materials.
Some more detailed descriptions of singlet emitters, triplet emitters, and TADF materials are provided below (but not limited thereto).
1. Singlet state luminophor
Singlet emitters tend to have longer conjugated pi-electron systems. Hitherto, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847, and triarylamine derivatives of pyrene disclosed in US7233019, KR 2006-0006760.
In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and arylamines.
A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9,10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 position of pyrene.
Examples, also preferred, of singlet emitters based on vinylamines and arylamines can be found in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B 2, DE 102005058557A 1, CN 1583691A, JP 08053397A, US 6251531B 1, US 2006/210830A, EP 1957606A 1 and US 2008/0113101A 1 and the entire contents of the patent documents listed above are hereby incorporated by reference.
An example of singlet emitters based on stilbene and its derivatives is US 5121029.
Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.
Further preferred singlet emitters may be selected from fluorene based fused ring systems as disclosed in US2015333277a1, US2016099411a1, US2016204355a 1.
More preferred singlet emitters may be selected from pyrene derivatives, such as the structures disclosed in US2013175509a 1; triarylamine derivatives of pyrene, such as pyrene triarylamine derivatives containing dibenzofuran units as disclosed in CN 102232068B; other triarylamine derivatives of pyrene having specific structures are disclosed in CN105085334A, CN 105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of anthracene, such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphene, xanthene, phenanthrene, pyrene, such as 2,5,8, 11-tetra-t-butylperylene, indenopyrene, phenylene, such as (4,4 '-bis (9-ethyl-3-carbazolyl-vinyl) -1, 1' -biphenyl, diindenopyrene, decacycloalkene, coronene, fluorene, spirobifluorene, arylpyrene, such as U.S. 20060222886, aryleneethene, such as U.S. Pat. No. 5121029, U.S. Pat. No. 5,8803, cyclopentadiene, such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans, such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) iminoboron compounds (US 2007/0092753 a1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and pyrrolopyrrolediones. Some singlet emitter materials can be found in the patent documents US 20070252517A 1, US 4769292, US 6020078, US 2007/0252517A 1, US 2007/0252517A 1. The entire contents of the above listed patent documents are hereby incorporated by reference.
Some examples of suitable singlet emitters are listed in the following table:
Figure BDA0002608371730000151
Figure BDA0002608371730000161
2. triplet emitter
Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) n, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer from 1 to 6. Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex. In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:
Figure BDA0002608371730000162
the metal atom M is selected from the transition metals or the lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W or Eu, particularly preferably Ir, Au, Pt, W or Os.
Ar4，Ar5Each occurrence, which may be the same or different, is a cyclic group wherein Ar4Contains at least one donor atom, i.e. an atom having a lone pair of electrons, such as nitrogen, which is coordinately bound to the metal via its cyclic group; wherein Ar is5Contains at least one carbon atom through which the cyclic group is attached to the metal; ar (Ar)4And Ar5Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0. Examples of organic ligands may be selected from phenylpyridine derivatives or 7, 8-benzoquinoline derivatives. All of these organic ligands may be substituted, for example, with alkyl or fluorine or silicon. The ancillary ligand may preferably be selected from acetone acetate or picric acid.
Examples of materials and their use for some triplet emitters can be found in patent documents and literature, WO200070655, WO200141512, WO200202714, WO200215645, WO2005033244, WO2005019373, US20050258742, US20070087219, US20070252517, US2008027220, WO2009146770, US20090061681, US20090061681, WO2009118087, WO2010015307, WO2010054731, WO2011157339, WO2012007087, WO 2012012012012012018, WO2013107487, WO2013094620, WO2013174471, WO 2014031977, WO 2014112450, WO2014007565, WO 2014024131, Baldo et al Nature (2000), 750, Adachi et al.Appl. Phys.Lett. (2001), 1622, Kido et al.Phyt. Phyt., Lett. (2001), Synrather et al.1994, American et al., Meth.1974, Meth., Meth.1978, and Met.1978 (Met et al). The entire contents of the above listed patent documents and literature are hereby incorporated by reference. Some examples of suitable triplet emitters are listed in the following table:
Figure BDA0002608371730000163
Figure BDA0002608371730000171
3. thermally activated delayed fluorescence luminescent material (TADF)
The traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (Δ Est), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.
TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.2eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials may be found in patent documents CN103483332(a), TW201309696(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et al.adv.mater, 21, 2009, 4802, Adachi, et al.appl.phyt.98, 2011, 083302, Adachi, et al.appl.phys.lect.98, 2011, 083302, Adachi, et al.phys.phys.101, 2012, 093306, Adachi, et al.chem.chemn.48, 35, 11392, Adachi, et al.natu photos, 6, 253, Adachi, nat 560, nat 560234, oram.20111, Adachi J. 19, Adachi et al.7, Adachi J. 103, Adachi J. 48, Adachi et al.103, Adachi J. 19, Adachi et al.103, Adachi j 29, Adachi et al.7, Adachi et al.103, Adachi et 3, adac. 73, Adachi et 3, Adachi et al.7, Adachi et al.103, Adachi et al.
Some examples of suitable TADF phosphors are listed below:
Figure BDA0002608371730000181
the device structure of the organic light emitting diode, including, but not limited to, the cathode, the anode, and the light extraction layer, will be described below.
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light emitting layer or the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The material of the light extraction layer needs to have a proper energy level structure, the light extraction layer has strong absorption in a region with the wavelength less than 400nm, and the absorption of visible light with the wavelength more than 400nm is weak or close to zero, so that the damage caused by the irradiation of high-energy light on the material in the device in the subsequent process is avoided. Meanwhile, the light extraction layer material has a higher refractive index, so that the emission of visible light can be beneficially led out, and the luminous efficiency of the organic electronic light-emitting device is improved. Since the influence of light interference is large when the reflectance of the interface between the light extraction layer material and the adjacent electrode is large, the refractive index of the light extraction layer material is preferably larger than that of the adjacent electrode, and the refractive index at 630nm may be 1.50 or more, more preferably 1.70 or more, and particularly preferably 1.80 or more.
In more preferred embodiments, the organic compound of the light extraction layer according to the organic electroluminescent device of the present invention has a thickness of generally 10nm to 200nm, preferably 20nm to 150nm, more preferably 30nm to 100nm, most preferably 40nm to 90 nm.
In some embodiments, the light extraction layer is disposed on a side of the cathode surface remote from the organic functional layer. In other embodiments, the light extraction layer is disposed on the anode surface and away from the organic functional layer.
The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The invention further relates to an organic compound selected from the structures represented by the general formula (4):
Figure BDA0002608371730000191
wherein:
L1and L3Each independently selected from a single bond, a substituted or unsubstituted aromatic or heteroaromatic group of 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system of 3 to 30 ring atoms;
L2selected from a single bond or the following groups:
Figure BDA0002608371730000192
W、W1each occurrence is independently selected from CR9Or N;
Y2、Y3each occurrence is independently selected from NR10、CR10R11、O、S、SiR10R11、S＝O、SO2Or PR10；
R9、R10And R11Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
In one embodiment of the present invention, the substrate is,
Figure BDA0002608371730000193
at least one W is selected from N. Further, the air conditioner is provided with a fan,
Figure BDA0002608371730000194
is selected from
Figure BDA0002608371730000195
Further, in the case of a liquid crystal display,
Figure BDA0002608371730000196
is selected from
Figure BDA0002608371730000197
The dotted line indicates the attachment site.
In one embodiment of the present invention, the substrate is,
Figure BDA0002608371730000198
wherein each occurrence of W is independently selected from CR9。
Further, in the present invention,
Figure BDA0002608371730000199
selected from any one of the following groups, the dotted line representing the attachment site:
Figure BDA00026083717300001910
in one embodiment of the present invention, the substrate is,
Figure BDA00026083717300001911
selected from any one of the following groups, the H atom on the ring may be further substituted, the dotted line representing the attachment site:
Figure BDA0002608371730000201
in one embodiment, formula (4) is selected from any one of formulae (5-1) to (5-6):
Figure BDA0002608371730000202
more preferably, W in the general formulae (5-1) to (5-6) is selected from CR9(ii) a More preferably, R9Is selected from H.
In one embodiment, L2Selected from a single bond or any of the following groups:
Figure BDA0002608371730000203
in one embodiment, L2Selected from a single bond or
Figure BDA0002608371730000204
In one embodiment, L2Selected from a single bond or
Figure BDA0002608371730000205
In one embodiment, L2Selected from single bonds or benzene; in one embodiment, L2Selected from single bonds.
In one embodiment, L1And L3Each independently selected from a single bond or any of the following groups:
Figure BDA0002608371730000206
wherein:
X2each occurrence is independently selected from CR6Or N;
Y1each occurrence is independently selected from NR7、CR7R8、O、S、SiR7R8、S＝O、SO2Or PR7；
R6、R7And R8Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
In one embodiment, L1And L3Each independently selected from any one of the following groups:
Figure BDA0002608371730000211
wherein: the H atoms on the ring may be further substituted.
In particular, L1、L2And L3Each independently selected from a single bond or any of the following groups, the dotted line representing the attachment site:
Figure BDA0002608371730000212
wherein: the H atoms on the ring may be further substituted.
In one embodiment, L1、L2And L3At least one of them is selected from single bonds; in one embodiment, L1、L2And L3At least two of which are selected from single bonds; in one embodiment, L1、L2And L3Are all selected from single bonds. In one embodiment, L1Is a single bond; in one embodiment, L3Is a single bond; in one embodiment, L1And L3Is a single bond;
in one embodiment, L1、L2And L3At least one is selected from benzene or naphthalene; in one embodiment, L1、L2And L3At least two are selected from benzene or naphthalene; in one embodiment, L1、L2And L3Are all selected from benzene or naphthalene.
In one embodiment, L1、L2And L3At least one is selected from benzene; in one embodiment, L1、L2And L3At least two benzenes; in one embodiment, L1、L2And L3Are all selected from benzene. In one embodiment, L3Is benzene; in one embodiment, L2Is benzene; in one embodiment, L1And L3Is benzene.
In one embodiment, L1、L2And L3Are all selected from single bonds or benzene; more preferably, at least one is selected from single bonds and at least one is selected from benzene; more preferably, one is selected from the group consisting ofA bond, two selected from benzene; more preferably, two are selected from single bonds and one is selected from benzene. In one embodiment, L1And L3Is a single bond, L2Is benzene.
Specifically, the organic compound according to the present invention is selected from any one of the structural formulae (G-145) to (G-211) as described above, but is not limited thereto.
The organic compounds according to the invention can be used not only in the light extraction layers of organic electronic devices but also in other organic functional layers, for example: an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, and a light emitting layer.
A light extraction layer material comprising an organic compound as described above.
It is an object of the present invention to provide a material solution for evaporation type OLEDs.
In certain embodiments, the organic compounds according to the present invention have a molecular weight of 1200g/mol or less, preferably 1100g/mol or less, very preferably 1000g/mol or less, more preferably 950g/mol or less, and most preferably 900g/mol or less.
The invention also relates to a composition comprising at least one organic compound shown as the general formula (4) and at least one organic solvent; the at least one organic solvent is selected from aromatic hydrocarbon or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.
The invention still further relates to an organic electronic device comprising at least one compound as described above. The organic electronic device according to the present invention may be selected from, but is not limited to, Organic Light Emitting Diodes (OLEDs), organic photovoltaic cells, organic light emitting cells, organic field effect transistors, organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors, organic plasmon emitting diodes, and the like, and particularly preferably is an OLED.
The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The synthesis of the compounds according to the invention is illustrated, but the invention is not limited to the following examples.
Figure BDA0002608371730000221
Synthesis of Compound C-1:
Figure BDA0002608371730000231
compound 1-1(4.86g, 15mmol), 1-2(8.16g, 30mmol), potassium carbonate (6.26g, 45mmol), tetrakis (triphenylphosphine) palladium (0.52g, 0.45mmol) were placed in a three-necked flask with toluene and methanol (volume ratio 3: 1), nitrogen was replaced three times, and the reaction was stirred while gradually raising the temperature to 80 ℃. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 4.19g of compound I-3 with a yield of 45%.
Compound 1-3(3.73g, 6mmol) was dissolved in anhydrous toluene, 1-4(0.92g, 6mmol), sodium tert-butoxide (1.73g, 18mmol) and tris-dibenzylideneacetone dipalladium (0.16g, 0.18mmol) were added thereto, nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.18mmol) was added thereto, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 2.88g of compound C-1 with a yield of 65%. 738.6 m/z
Synthesis of Compound C-2:
Figure BDA0002608371730000232
compound 2-1(2.6g, 9.7mmol) and 2-2(7.7g,25.2mmol) were dissolved in 100mL of anhydrous toluene, sodium tert-butoxide (4.8g, 50mmol) and tris-dibenzylideneacetone dipalladium (0.28g, 0.3mmol) were added, nitrogen was replaced three times, and then tri-tert-butylphosphine (0.3mmol) was added, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 5.6g of compound C-2 with a yield of 72%. 678.5 m/z
Synthesis of Compound C-3:
Figure BDA0002608371730000233
compound 3-1(3.1g, 10.9mmol) and 2-2(7.3g, 24mmol) were dissolved in anhydrous toluene, and sodium tert-butoxide (4.8g, 50mmol) and tris-dibenzylideneacetone dipalladium (0.28g, 0.3mmol) were added after nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.3mmol) was added, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 4.2g of compound C-3 with a yield of 53%. 737.3 m/z
Synthesis of Compound C-4:
Figure BDA0002608371730000241
4-1(10g, 58mmol) and 4-2(8.9g, 58mmol) were placed in polyphosphoric acid, heated to 160 ℃ and stirred for about 12 hours. After cooling to room temperature, sodium hydroxide aqueous solution was added at low temperature for neutralization, and 14.3g of intermediate 4-3 was obtained by suction filtration under reduced pressure, with a yield of 85%.
Intermediate 4-3(14.3g, 9.7mmol) was dissolved in 100mL of a mixed solution of tetrahydrofuran and methanol, and 3 times the amount of selenious chloride dihydrate (6.75g, 30mmol) was added thereto, and the temperature was raised to 70 ℃. Stirring and reacting for 12 hours, adding a sodium bicarbonate aqueous solution after the system is cooled, extracting with ethyl acetate, combining organic phases, and drying with anhydrous sodium sulfate. Concentration through a silica gel column under reduced pressure gave 9.5g in total of intermediate 4-4 in 74% yield.
Intermediate 4-4(5g, 19.2mmol) and 2-2(12.8g, 42mmol) were dissolved in 80mL of anhydrous toluene, and sodium tert-butoxide (5.8g, 60mmol) and tris-dibenzylideneacetone dipalladium (0.55g, 0.6mmol) were added after nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.6mmol) was added, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 6.2g of compound C-4 with a yield of 45%. m/z is 712.5
Synthesis of Compound C-5:
Figure BDA0002608371730000242
9-phenanthreneboronic acid (13g, 58.5mmol), p-bromoaniline (10g, 58.5mmol), potassium carbonate (73g, 175mmol) and tetrakis (triphenylphosphine) palladium (2g, 1.76mmol) were placed in a three-necked flask with toluene and methanol (volume ratio 3: 1), nitrogen was replaced three times, the temperature was gradually raised to 80 ℃, and the reaction was stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 13.5g in total of intermediate 5-1, yield 86%.
Compound 5-1(10g, 37.1mmol) and 2-2(11.35g, 37.1mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (10.7g, 111mmol) and tris-dibenzylideneacetone dipalladium (1g, 1.11mmol) were added, nitrogen gas was replaced three times, and tri-tert-butylphosphine (1.11mmol) was added, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 10.3g in total of intermediate 5-2, with a yield of 56%.
Compound 5-2(8g, 16.2mmol) and compound 5-3(3.8g, 16.2mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (4.7g, 48.6mmol) and tris-dibenzylideneacetone dipalladium (0.41g, 0.5mmol) were added, nitrogen gas was replaced three times, and then tri-tert-butylphosphine (0.5mmol) was added, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 8.2g of compound C-5 in a yield of 78% in total. m/z 648.9
Synthesis of Compound C-6:
Figure BDA0002608371730000251
compounds 6-1(8g, 36.4mmol) and 6-2(14.3g, 36.4mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (10.5g, 109mmol) and tris-dibenzylideneacetone dipalladium (1g, 1.1mmol) were added thereto, nitrogen gas was replaced three times, and tri-tert-butylphosphine (1.1mmol) was added thereto, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 9.2g in total of intermediate 6-3, yield 47%.
Compounds No. 6-3(6g, 11.2mmol) and 2-2(3.43g, 11.2mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (3.3g, 33.6mmol) and tris-dibenzylideneacetone dipalladium (0.31g, 0.34mmol) were added thereto, nitrogen gas was replaced three times, and then, tri-tert-butylphosphine (0.34mmol) was added thereto, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 6.6g of compound C-6 with a yield of 77%. 761.2 m/z
Synthesis of Compound C-7:
Figure BDA0002608371730000252
compound 7-1(1.7g, 6.1mmol) and 5-2(3g, 6.1mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.76g, 18.3mmol) and tris-dibenzylideneacetone dipalladium (0.17g, 0.18mmol) were added, nitrogen gas was replaced three times, and then tri-tert-butylphosphine (0.18mmol) was added, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 3.6g of compound C-7 with a yield of 86%. 688.7 m/z
Synthesis of Compound C-8:
Figure BDA0002608371730000253
compound 8-1(2.9g, 20mmol) and 2-2(6.12g, 20mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (5.76g, 60mmol) and dibenzylideneacetone dipalladium (0.55g, 0.6mmol) were added thereto, nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.6mmol) was added thereto, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 4.58g in total of intermediate 8-2, yield 62%.
The intermediate 8-3(3.79g, 12mmol) and 8-2(4.43g, 12mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (3.46g, 36mmol) and dibenzylideneacetone dipalladium (0.33g, 0.36mmol) were added thereto, nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.36mmol) was added thereto, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 5.37g of compound C-8 with a yield of 69%. 649.9 m/z
Synthesis of Compound C-9:
Figure BDA0002608371730000261
compound 9-1(2.89g, 10mmol) and 5-2(4.95g, 10mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (2.88g, 30mmol) and dibenzylideneacetone dipalladium (0.28g, 0.3mmol) were added thereto, nitrogen gas was replaced three times, tri-tert-butylphosphine (0.3mmol) was added thereto, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through silica gel to obtain 5.98g of compound C-9 with a yield of 85%. 704.6 m/z
Synthesis of Compound C-10:
Figure BDA0002608371730000262
compound 10-1(2.38g, 8mmol) and 2-2(5.51g, 18mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (2.3g, 24mmol) and dibenzylideneacetone dipalladium (0.22g, 0.24mmol) were added thereto, nitrogen gas was replaced three times, tri-tert-butylphosphine (0.24mmol) was added thereto, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 3.30g of compound C-10 in 55% yield. 749.7 m/z
Synthesis of Compound C-11:
Figure BDA0002608371730000263
compound 11-1(4.79g, 15mmol) and 2-2(4.59g, 15mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (4.32g, 45mmol) and dibenzylideneacetone dipalladium (0.41g, 0.45mmol) were added thereto, nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.45mmol) was added thereto, and the reaction was gradually warmed to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 4.74g of intermediate 11-2 in total, with a yield of 58%.
Intermediate 11-2(4.36g, 8mmol) and intermediate 11-3(1.82g, 8mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (2.30g, 24mmol) and tris-dibenzylideneacetone dipalladium (0.22g, 0.24mmol) were added thereto, nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.24mmol) was added thereto, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 2.65g of compound C-11 with a yield of 45%. 737.7 m/z
Synthesis of Compound C-12:
Figure BDA0002608371730000264
intermediate 11-2(4.36g, 8mmol) and intermediate 12-1(2.32g, 8mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (2.30g, 24mmol) and tris-dibenzylideneacetone dipalladium (0.22g, 0.24mmol) were added thereto, nitrogen gas was replaced three times, and then tri-tert-butylphosphine (0.24mmol) was added thereto, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 4.58g of compound C-12 with a yield of 76%. 754.5 m/z
Synthesis of Compound C-13:
Figure BDA0002608371730000271
compound 1-1(6.5g, 20mmol), 13-1(10.88g, 40mmol), potassium carbonate (8.34g, 60mmol), tetrakis (triphenylphosphine) palladium (0.69g, 0.6mmol) were placed in a three-necked flask with toluene and methanol (volume ratio 3: 1), nitrogen was replaced three times, and the temperature was gradually raised to 80 ℃ and the reaction was stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 9.44g of intermediate 13-2 in total, with a yield of 76%.
Compound 13-2(6.21g, 10mmol) was dissolved in anhydrous toluene, and 7-1(2.73g, 10mmol), sodium tert-butoxide (2.88g, 30mmol) and tris-dibenzylideneacetone dipalladium (0.28g, 0.3mmol) were added thereto, and after nitrogen gas was replaced three times, tri-tert-butylphosphine (0.3mmol) was added, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 5.54g of compound C-13 in 68% yield. 814.3 m/z
Synthesis of Compound C-14:
Figure BDA0002608371730000272
compound 14-1(2.1g, 10mmol), 2-bromotriphenylene (3.06g, 10mmol) were dissolved in anhydrous toluene, and sodium tert-butoxide (2.88g, 30mmol) and tris-dibenzylideneacetone dipalladium (92mg, 0.1mmol) were added after nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.1mmol) was added, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 2.7g of compound 14-2 with a yield of 62%.
Compound 14-2(2.6g, 6mmol), 3-bromo-1, 10-phenanthroline (1.55g, 6mmol) were dissolved in anhydrous toluene, sodium tert-butoxide (1.73g, 18mmol) and tris-dibenzylideneacetone dipalladium (55mg, 0.06mmol) were added after nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.06mmol) was added, and the reaction was gradually heated to 110 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column to obtain 1.7g of compound C-14 with a yield of 46%. 615.2 m/z
Synthesis of Compound C-15:
Figure BDA0002608371730000281
compound 15-1(3.3g, 15mmol), 2-bromotriphenylene (4.6g, 15mmol) were dissolved in anhydrous toluene, and sodium tert-butoxide (4.32g, 45mmol) and tris-dibenzylideneacetone dipalladium (0.14g, 0.15mmol) were added after nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.15mmol) was added, and the reaction was gradually heated to 80 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column 4.74g of compound 15-2, yield 71%.
Compounds 15-2(4.45g, 10mmol) and 15-3(2.75g, 10mmol) were dissolved in anhydrous toluene, and sodium tert-butoxide (2.88g, 30mmol) and tris-dibenzylideneacetone dipalladium (92mg, 0.1mmol) were added after nitrogen gas was replaced three times, and tri-tert-butylphosphine (0.01mmol) was added, and the reaction was gradually heated to 110 ℃ and stirred. After TLC spot plate reactant disappeared, remove the heat source. After the system was cooled, water was added, the organic layer was separated, extracted three times with ethyl acetate, concentrated under reduced pressure, and passed through a silica gel column 2.43g of compound C-15 with a yield of 38%. 641.2 m/z
Extinction system and refractive index calculation
The compound is evaporated on the monocrystalline silicon by a vacuum evaporation mode to form a 50nm thin film, the monocrystalline silicon is placed on a sample stage of an ellipsometer (ES-01), the incident angle is 70 degrees, the test is in an atmospheric environment, and the test result of the extinction coefficient (k) and the refractive index (n) of the compound is obtained by fitting the ellipsometer.
The results are shown in table 1:
TABLE 1
Figure BDA0002608371730000282
The compound of the invention has weak absorption in visible light wave band and higher absorption in ultraviolet wave band, and can resist the damage of external high-energy light to the inside of the device. A higher refractive index ensures a better light extraction effect.
Preparation and characterization of OLED device
The following describes in detail the fabrication process of the OLED device using the above embodiments, and as shown in fig. 1, the structure of the OLED device is as follows: ITO/Ag/ITO (anode)/HATCN/SFNFB/m-CP Ir (p-ppy)3/NaTzF2Ag/light extraction layer/LiF/Mg, the preparation steps are as follows:
cleaning the ITO conductive glass anode layer, ultrasonically cleaning the ITO conductive glass anode layer for 15 minutes by using deionized water, acetone and isopropanol, and then cleaning the ITO conductive glass anode layer in a plasma cleanerAnd (5) treating for 5 minutes to improve the work function of the electrode. Evaporating a hole injection layer material HATCN on the ITO anode layer by a vacuum evaporation mode, wherein the thickness is 5nm, and the evaporation rate is high
Figure BDA0002608371730000283
On the hole injection layer, a hole transport material SFNFB was deposited by vacuum evaporation to a thickness of 80 nm. Depositing a light emitting layer on the hole transport layer, m-CP as a host material, Ir (p-ppy)3As doping material, Ir (p-ppy)3And m-CP in a mass ratio of 1:9 and a thickness of 30 nm. Depositing electron transport material NaTzF on the luminescent layer by vacuum evaporation2And the thickness is 30 nm. On the electron transport layer, an electron injection layer LiF with a thickness of 1nm was vacuum-evaporated, which was an electron injection layer 7. And (3) vacuum evaporating a cathode Mg-Ag layer on the electron injection layer, wherein the doping ratio of Mg to Ag is 9:1, and the thickness is 15 nm. On the cathode layer, a light extraction layer compound C-2 was deposited by vacuum deposition to a thickness of 60 nm.
Device example 2: the compound of the light extraction layer of the organic electroluminescent device was changed to C-3.
Device example 3: the compound of the light extraction layer of the organic electroluminescent device was changed to C-6.
Device example 4: the compound of the light extraction layer of the organic electroluminescent device was changed to C-7.
Device example 5: the compound of the light extraction layer of the organic electroluminescent device was changed to C-9.
Device example 6: the compound of the light extraction layer of the organic electroluminescent device becomes C-10.
Device example 7: the compound of the light extraction layer of the organic electroluminescent device was changed to C-11.
Device example 8: the compound of the light extraction layer of the organic electroluminescent device was changed to C-12.
Device example 9: the compound of the light extraction layer of the organic electroluminescent device was changed to C-13.
Device example 10: the compound of the light extraction layer of the organic electroluminescent device becomes C-1.
Device example 11: the compound of the light extraction layer of the organic electroluminescent device becomes C-4.
Device example 12: the compound of the light extraction layer of the organic electroluminescent device was changed to C-5.
Device example 13: the compound of the light extraction layer of the organic electroluminescent device was changed to C-8.
Device example 14: the compound of the light extraction layer of the organic electroluminescent device becomes C-14.
Device example 15: the compound of the light extraction layer of the organic electroluminescent device was changed to C-15.
Device comparative example 1: the light extraction layer compound of the organic electroluminescent device becomes CBP.
The structures of the compounds involved in the devices are as follows:
Figure BDA0002608371730000291
TABLE 2
Numbering Light extraction layer compound Luminous efficiency (cd/A)
Device example 1 C-2 1.24
Device example 2 C-3 1.12
Device example 3 C-6 1.09
Device example 4 C-7 1.25
Device example 5 C-9 1.15
Device example 6 C-10 1.09
Device example 7 C-11 1.05
Device example 8 C-12 1.17
Device example 9 C-13 1.21
Device example 10 C-1 1.12
Device example 11 C-4 1.13
Device example 12 C-5 1.04
Device example 13 C-8 1.06
Device example 14 C-14 1.11
Device example 15 C-15 1.12
Comparative example 1 CBP 1
In Table 2, the luminous efficiency is a current density of 10mA/cm2The relative values obtained. It can be seen from table 2 that the compounds of the present invention can effectively improve the light emitting efficiency of the organic electroluminescent device as a light extraction layer in comparison with the comparative ratio. Furthermore, the organic electroluminescent device using C-2, C-7, C-12 and C-13 as the light extraction layer in the compound of the invention has better luminous efficiency.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (14)

1. An organic electroluminescent device comprising two electrodes, one or more organic functional layers disposed between the two electrodes, and a light extraction layer disposed on a surface of one of the electrodes and on a side away from the organic functional layer, characterized in that: the light extraction layer material contains a compound represented by general formula (1):
Figure FDA0002608371720000011
wherein:
L1、L2and L3Each independently selected from a single bond, a substituted or unsubstituted aromatic or heteroaromatic group of 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system of 3 to 30 ring atoms;
Ar1selected from electron withdrawing groups; ar (Ar)2Selected from substituted or unsubstituted condensed ring aromatic group or condensed ring hetero aromatic group with 10-30 ring atoms;
v is independently selected from CR at each occurrence1Or N;
R1each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
2. According to the rightThe organic electroluminescent device according to claim 1, wherein: ar (Ar)2Any one group selected from (A-1) to (A-5):
Figure FDA0002608371720000012
wherein:
x is independently selected from CR at each occurrence2Or N;
R2each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
3. The organic electroluminescent device according to claim 2, characterized in that: the general formula (1) is selected from any one of the structures of general formulas (2-1) to (2-4):
Figure FDA0002608371720000021
4. the organic electroluminescent device according to claim 1, wherein: ar (Ar)1Selected from any one of the following groups:
Figure FDA0002608371720000022
wherein:
X1each occurrence is independently selected from CR3Or N, and at least one X1Is selected from N;
each occurrence of Y is independently selected from NR4、CR4R5、O、S、SiR4R5、S＝O、SO2Or PR4；
R3、R4And R5Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
5. The organic electroluminescent device according to claim 4, wherein: ar (Ar)1Selected from any one of the following groups:
Figure FDA0002608371720000023
6. the organic electroluminescent device according to claim 4, wherein: the general formula (1) is selected from general formula (3-1) or (3-2):
Figure FDA0002608371720000024
wherein:
x is independently selected from CR at each occurrence2Or N;
R2each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
7. The organic electroluminescent device according to claim 1, wherein L1、L2And L3Each independently selected from a single bond or any of the following groups:
Figure FDA0002608371720000031
wherein:
X2each occurrence is independently selected from CR6Or N;
Y1each occurrence is independently selected from NR7、CR7R8、O、S、SiR7R8、S＝O、SO2Or PR7；
R6、R7And R8Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.
8. The organic electroluminescent device according to claim 7, wherein L1、L2And L3Each independently selected from a single bond or benzene.
9. The organic electroluminescent device according to any one of claims 1 to 8, wherein: the refractive index of the material of the light extraction layer at the wavelength of 630nm is greater than 1.7; and/or
The extinction coefficient of the material of the light extraction layer is less than 0.1 at a wavelength of 430 nm.
10. The organic electroluminescent device according to any one of claims 1 to 8, wherein: the organic electroluminescent device is an organic light emitting diode, wherein the light extraction layer is located on a cathode surface of the organic light emitting diode.
11. An organic compound characterized by: selected from the structures represented by the general formula (4):
Figure FDA0002608371720000032
wherein:
L1and L3Each independently selected from a single bond, a substituted or unsubstituted aromatic or heteroaromatic group of 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring system of 3 to 30 ring atoms;
L2selected from a single bond or any of the following groups:
Figure FDA0002608371720000033
W、W1each occurrence is independently selected from CR9Or N;
Y2、Y3each occurrence is independently selected from NR10、CR10R11、O、S、SiR10R11、S＝O、SO2Or PR10；
R9、R10And R11Each occurrence is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3Cl, Br, F, crosslinkable radicals, having from 5 to 60 ring atomsSubstituted or unsubstituted aromatic groups, substituted or unsubstituted heteroaromatic groups having 5 to 60 ring atoms, aryloxy groups having 5 to 60 ring atoms, heteroaryloxy groups having 5 to 60 ring atoms, or combinations of these groups.
12. An organic compound according to claim 11, characterized in that: the general formula (4) is selected from any one of general formulae (5-1) to (5-6):
Figure FDA0002608371720000041
13. a composition comprising at least one organic compound according to any one of claims 11 to 12, and at least one organic solvent.
14. A light extraction layer material comprising the organic compound according to any one of claims 11 to 12.
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