CN112652730A - Composition and organic electroluminescent element comprising same - Google Patents

Composition and organic electroluminescent element comprising same Download PDF

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CN112652730A
CN112652730A CN202011571783.0A CN202011571783A CN112652730A CN 112652730 A CN112652730 A CN 112652730A CN 202011571783 A CN202011571783 A CN 202011571783A CN 112652730 A CN112652730 A CN 112652730A
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王子兴
陈清泉
吕伯彦
吴空物
赵晓宇
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Zhejiang Huadisplay Optoelectronics Co Ltd
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Abstract

The invention belongs to the field of organic photoelectricity, and particularly relates to a composition containing an iridium metal complex and an organic compound and an organic electroluminescent element containing the composition, in particular to an organic electroluminescent diode, wherein the iridium metal complex has a structure shown in a formula (I), and the organic compound has a structural formula (II) or (III):
Figure DDA0002862937380000011
in the iridium metal complex formula (I), (L ^ Z) is selected from a formula (IV),

Description

Composition and organic electroluminescent element comprising same
Technical Field
The invention belongs to the field of organic electroluminescence, and particularly relates to a composition of an iridium metal complex and an organic compound, and an organic electroluminescent element containing the composition.
Background
As a novel display technology, the organic electroluminescent element has the unique advantages of self luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, high response speed, wide application temperature range, low driving voltage, capability of manufacturing flexible, bendable and transparent display panels, environmental friendliness and the like, can be applied to flat panel displays and new generation illumination, and can also be used as a backlight source of an LCD.
Since the invention of the 20 th century and the 80 th century, organic electroluminescent devices have been used in industry, such as display screens of mobile phones, but the current OLED devices have limited their wider application, especially large screen displays, due to low efficiency and short service life. And the most important factor restricting the wide application thereof is the performance of the organic electroluminescent material. Meanwhile, when an OLED device is operated by applying a voltage, joule heat is generated, so that organic materials are easily crystallized, and the lifetime and efficiency of the device are affected.
Since the ratio of the singlet excited state to the triplet excited state due to charge binding is theoretically estimated to be 1:3, the use of a small molecular fluorescent material is considered to be only 25% of the total energy available for light emission, and the remaining 75% of the energy is lost due to the non-light-emitting mechanism of the triplet excited state, so that the internal quantum efficiency limit of the fluorescent material is considered to be 25%. Professor Baldo and Forrest in 1998 discovered that triplet phosphorescence can be utilized at room temperature, and the upper limit of the original internal quantum efficiency is raised to 100%, and triplet phosphors are complex compounds composed of heavy metal atoms, and by utilizing the heavy atom effect, the strong spin-orbit coupling effect causes the energy levels of singlet excited states and triplet excited states to be mixed with each other, so that the originally forbidden triplet energy is relieved to emit light in the form of phosphorescence, and the quantum efficiency is greatly improved.
At present, almost all light emitting layers in an organic OLED module use a host-guest light emitting system mechanism, that is, a guest light emitting material is doped in a host material, and generally, the energy system of the organic host material is larger than that of the guest material, that is, the energy is transferred from the host to the guest, so that the guest material is excited to emit light. A commonly used phosphorescent organic host material such as CBP (4, 4' -bis (9-carbazolyl) -biphenyl) has a high efficiency and a high triplet energy level, and when it is used as an organic material, the triplet energy can be efficiently transferred from a light emitting organic material to a guest phosphorescent light emitting material. A commonly used organic guest material is an iridium metal complex.
The invention discovers that the combination of a specific organic compound and an iridium metal compound can be used as a light-emitting layer of an organic electroluminescent element to remarkably improve the current efficiency of the organic electroluminescent element, reduce the operating voltage of the element and prolong the service life of the element.
Disclosure of Invention
The invention aims to provide a composition of an iridium metal complex and an organic compound and an organic electroluminescent element comprising the composition.
The invention provides a composition of an iridium metal complex and an organic compound, wherein the iridium metal complex has a structure shown in a formula (I), and the organic compound has a structural formula (II) or (III):
Figure BDA0002862937360000021
preferably, in formula (I), X is selected from NR1, O, S, CR1R2, SiR1R2, O ═ P-R1 or B-R1; y is selected from N or C-R1;
(L ^ Z) is selected from structural formulas represented by the formula (IV),
Figure BDA0002862937360000022
R1-R8, R11 are independently selected from any one of hydrogen, deuterium, cyano, halogen, C1-C18 alkyl, C1-C18 alkoxy, C1-C18 alkylsilyl, C1-C18 alkoxysilyl, C6-C40 aryl, C1-C40 heteroaryl, substituted or unsubstituted arylether group, substituted or unsubstituted heteroarylether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilicon group, substituted or unsubstituted heteroarylsilicon group, substituted or unsubstituted aryloxyside group, substituted or unsubstituted arylacyl group, substituted or unsubstituted heteroarylacyl group, substituted or unsubstituted phosphinyl group; r9, R10 are selected fromAny one of cyano, C1-C18 alkyl, C1-C18 alkoxy, C6-C40 aryl, C1-C40 heteroaryl, substituted or unsubstituted aryl ether group, substituted or unsubstituted heteroaryl ether group, substituted or unsubstituted aryl acyl, substituted or unsubstituted heteroaryl acyl and substituted or unsubstituted phosphinyl; all groups may be partially deuterated or fully deuterated. m is taken from 1 or 2, and m + n is 3; heteroaryl means containing B, N, O, S, P (═ O), Si, P at least one heteroatom;
in formula (II) and formula (III), X1 to X6 are CR or N; y1 to Y8 are CR or N, and at least 2 are N; l is absent or selected from single bond, O, S, CRR, SiRR, NR; a and B are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; r is independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, aryl or heteroaryl substituted amine; n is an integer of 0 to 6; adjacent X or Y may form a ring; all groups may be partially deuterated or fully deuterated.
Preferably, R1 to R11 in the iridium metal complex of the present invention are selected from one of the following representative structural formulae, but do not represent and are not limited thereto:
Figure BDA0002862937360000031
preferably, the iridium metal complex of the present invention is selected from one of the following structures, but does not represent a limitation thereto:
Figure BDA0002862937360000041
Figure BDA0002862937360000051
Figure BDA0002862937360000061
Figure BDA0002862937360000071
Figure BDA0002862937360000081
Figure BDA0002862937360000091
Figure BDA0002862937360000101
Figure BDA0002862937360000111
Figure BDA0002862937360000121
Figure BDA0002862937360000131
Figure BDA0002862937360000141
Figure BDA0002862937360000151
Figure BDA0002862937360000161
Figure BDA0002862937360000171
Figure BDA0002862937360000181
Figure BDA0002862937360000191
Figure BDA0002862937360000201
Figure BDA0002862937360000211
Figure BDA0002862937360000221
Figure BDA0002862937360000231
Figure BDA0002862937360000241
Figure BDA0002862937360000251
the invention provides a composition, wherein when the structure of the organic compound is shown as the formula (II), the organic compound is preferably selected from the compounds II-1 to II-7,
but are not meant to be limited thereto:
Figure BDA0002862937360000261
wherein X1 to X6, L, A, B, R, n are the same as described above.
Preferably, a and B are selected from the group described by the following structures, but do not represent a limitation thereto:
Figure BDA0002862937360000262
wherein X1 to X6, Y1 to Y8, L, R, n are the same as described above.
Preferably, one organic compound represented by formula (II) or formula (III) is selected from at least one of the following representative structures, but does not represent a limitation thereto:
Figure BDA0002862937360000271
Figure BDA0002862937360000281
Figure BDA0002862937360000291
Figure BDA0002862937360000301
Figure BDA0002862937360000311
Figure BDA0002862937360000321
Figure BDA0002862937360000331
Figure BDA0002862937360000341
Figure BDA0002862937360000351
Figure BDA0002862937360000361
Figure BDA0002862937360000371
Figure BDA0002862937360000381
Figure BDA0002862937360000391
Figure BDA0002862937360000401
Figure BDA0002862937360000411
Figure BDA0002862937360000421
Figure BDA0002862937360000431
Figure BDA0002862937360000441
Figure BDA0002862937360000451
Figure BDA0002862937360000461
Figure BDA0002862937360000471
Figure BDA0002862937360000481
Figure BDA0002862937360000491
Figure BDA0002862937360000501
Figure BDA0002862937360000511
Figure BDA0002862937360000521
Figure BDA0002862937360000531
Figure BDA0002862937360000541
Figure BDA0002862937360000551
Figure BDA0002862937360000561
Figure BDA0002862937360000571
Figure BDA0002862937360000581
Figure BDA0002862937360000591
Figure BDA0002862937360000601
Figure BDA0002862937360000611
Figure BDA0002862937360000621
Figure BDA0002862937360000631
Figure BDA0002862937360000641
Figure BDA0002862937360000651
Figure BDA0002862937360000661
Figure BDA0002862937360000671
Figure BDA0002862937360000681
Figure BDA0002862937360000691
Figure BDA0002862937360000701
Figure BDA0002862937360000711
Figure BDA0002862937360000721
Figure BDA0002862937360000731
Figure BDA0002862937360000741
Figure BDA0002862937360000751
Figure BDA0002862937360000761
Figure BDA0002862937360000771
Figure BDA0002862937360000781
Figure BDA0002862937360000791
Figure BDA0002862937360000801
Figure BDA0002862937360000811
Figure BDA0002862937360000821
Figure BDA0002862937360000831
Figure BDA0002862937360000841
the solvent used in the present invention is not particularly limited, and examples thereof include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decahydronaphthalene, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc., halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, etc., ether solvents such as tetrahydrofuran, tetrahydropyran, etc., ester solvents such as alkyl benzoate, etc., which are well known to those skilled in the art.
The present invention also relates to an organic opto-electronic device comprising: a first electrode;
a second electrode facing the first electrode;
the organic functional layer is clamped between the first electrode and the second electrode;
wherein the light-emitting layer comprises the composition.
The mass percentage of the iridium metal complex in the formula (I) in the light-emitting layer of the organic electroluminescent device is 0.1-50%.
In the present invention, the organic electroluminescent element is an anode which can be formed by depositing metal, an oxide having conductivity, or an alloy thereof on a substrate by a sputtering method, electron beam evaporation, vacuum deposition, or the like; and sequentially evaporating a hole injection layer, a hole transport layer, a luminescent layer, a hole blocking layer and an electron transport layer on the surface of the prepared anode, and then evaporating a cathode. The organic electroluminescent device is prepared by vapor deposition of the cathode, the organic layer and the anode on the substrate except the above method. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer. In the invention, the organic layer is prepared by adopting a high polymer material according to a solvent engineering (spin-coating), tape-casting (tape-casting), doctor-blading (sector-Printing), Screen-Printing (Screen-Printing), ink-jet Printing or Thermal-Imaging (Thermal-Imaging) method instead of an evaporation method, so that the number of the device layers can be reduced.
The materials used for the organic electroluminescent element according to the present invention may be classified into top emission, bottom emission, or double-sided emission. The compounds of the organic electroluminescent device according to the embodiment of the present invention can be applied to the aspects of the organic electroluminescent element such as an organic light emitting cell, an illuminating OLED, a flexible OLED, an organic photoreceptor, an organic thin film transistor and the like in a similar principle to the organic light emitting device.
The invention has the beneficial effects that:
the invention relates to a novel iridium metal complex and an organic compound composition, which have better thermal stability, the organic compound can balance the transport of holes and electrons, and the energy transmission between the organic compound and the iridium metal complex in the composition is more efficient.
Drawings
FIG. 1 is a structural diagram of an organic electroluminescent diode device according to the present invention.
Where 110 denotes a substrate, 120 denotes an anode, 130 denotes a hole injection layer, 140 denotes a hole transport layer, 150 denotes a light emitting layer, 160 denotes a hole blocking layer, 170 denotes an electron transport layer, 180 denotes an electron injection layer, and 190 denotes a cathode.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. 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 a preferred embodiment of the present invention, the OLED device according to the invention comprises a hole transport layer, which may preferably be selected from known or unknown materials, particularly preferably from the following structures, without representing the present invention being limited to the following structures:
Figure BDA0002862937360000861
in a preferred embodiment of the present invention, the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants. Preferred p-type dopants of the present invention are, but do not represent a limitation of the present invention to:
Figure BDA0002862937360000862
in a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the compounds ET-1 to ET-13, but does not represent that the present invention is limited to the following structures:
Figure BDA0002862937360000871
the organic compounds referred to in the present invention are obtained by known synthetic methods.
The general synthesis steps of the iridium metal complex related to the formula (I) are as follows:
Figure BDA0002862937360000872
the general procedure is as follows,
(1) ligand 1(0.10 mol), IrCl are added under the protection of argon3.3H2Heating and refluxing a mixed solution of O (0.045 mol), 2-ethoxyethanol (300 ml) and water (100 ml) for 16-20 hours until a supernatant is obtained, detecting the content of the ligand 1 by using high performance liquid chromatography to be less than 5%, stopping heating, cooling to room temperature, performing suction filtration by using a Buchner funnel, leaching a filter cake by using a mixed solution of water and 2-ethoxyethanol, and drying to obtain a bridging dimer 2 or 3 of yellow powder, wherein the yield is 81-89%.
(2) Under the protection of argon, dropwise adding a tetrahydrofuran solution of a dichloro crosslinked dimer complex (2.2mmol) into a lithium salt solution (-78 ℃) formed by a ligand L ^ Z (2.4mmol) and butyllithium, slowly heating to room temperature, heating under reflux for 6 hours, stopping heating, cooling to room temperature, adding a proper amount of distilled water, and filtering to obtain a solid. The solid was dissolved in dichloromethane and passed through a short column of silica gel. Removing the solvent under reduced pressure, and washing the solid obtained by concentration with methanol and petroleum ether in sequence to obtain the final target product.
Ligand 1 was obtained by custom synthesis. These are merely examples illustrating embodiments of the present invention and the scope of the present invention is not limited thereto.
Example 1: synthesis of Compound 1
Figure BDA0002862937360000881
Referring to the general synthetic route, lithium NN-dimethyl-phenylamidinate was used as lithium reagent in a yield of 70% of the final product. Mass spectrum m/z, theoretical 941.4; found M + H: 942.4.
example 2: synthesis of Compound 2
Figure BDA0002862937360000882
Referring to the general synthetic route, lithium NN-diethyl-phenylamidinate was used as lithium reagent in 75% yield of the final product. Mass spectrum m/z, theoretical 1081.51; found M + H: 1082.5.
example 3: synthesis of Compound 3
Figure BDA0002862937360000883
Referring to the general synthetic route, lithium NN-diisopropyl-phenylamidinate was used as lithium reagent in 76% yield of the final product. Mass spectrum m/z, theoretical 1025.5; found M + H: 1026.5.
example 4: synthesis of Compound 4
Figure BDA0002862937360000891
Referring to the general synthetic route, lithium NN-di-tert-butyl-phenylamidinate was used as lithium reagent in 72% yield of the final product. Mass spectrum m/z, theoretical 1165.6; found M + H: 1166.6.
example 5: synthesis of Compound 5
Figure BDA0002862937360000892
Referring to the general synthetic route, lithium NN-dimethyl-phenylamidinate was used as lithium reagent in 80% yield of the final product. Mass spectrum m/z, theoretical 947.34; found M + H: 948.3.
example 6: synthesis of Compound 6
Figure BDA0002862937360000893
Referring to the general synthetic route, lithium NN-diethyl-phenylamidinate was used as lithium reagent in 80% yield of the final product. Mass spectrum m/z, theoretical 1089.49; found M + H: 1090.5.
example 7: synthesis of Compound 7
Figure BDA0002862937360000894
Referring to the general synthetic route, lithium NN-isopropyl-phenylamidinate was used as lithium reagent in 73% yield of the final product. Mass spectrum m/z, theoretical 1031.43; found M + H: 1032.4.
example 8: synthesis of Compound 8
Figure BDA0002862937360000901
Referring to the general synthetic route, lithium NN-tert-butyl-phenylamidinate was used as lithium reagent in 68% yield of the final product. Mass spectrum m/z, theoretical 1143.56; found M + H: 1144.6.
example 9: synthesis of Compound 9
Figure BDA0002862937360000902
Referring to the general synthetic route, lithium NN-dimethyl-phenylamidinate was used as lithium reagent in 83% yield of the final product. Mass spectrum m/z, theoretical 1033.36; found M + H: 1034.4.
example 10: synthesis of Compound 10
Figure BDA0002862937360000903
Referring to the general synthetic route, lithium NN-diethyl-phenylamidinate was used as lithium reagent in 69% yield of the final product. Mass spectrum m/z, theoretical 1229.57; found M + H: 1230.5.
example 11: synthesis of Compound 11
Figure BDA0002862937360000904
Referring to the general synthetic route, lithium NN-diisopropyl-phenylamidinate was used as lithium reagent in 78% yield of the final product. Mass spectrum m/z, theoretical 1117.47; found M + H: 1118.4.
example 12: synthesis of Compound 12
Figure BDA0002862937360000911
Referring to the general synthetic route, lithium NN-di-tert-butyl-phenylamidinate was used as lithium reagent in 83% yield of the final product. Mass spectrum m/z, theoretical 1257.62; found M + H: 1258.6.
example 13: synthesis of Compound 13
Figure BDA0002862937360000912
Referring to the general synthetic route, lithium NN-dimethyl-phenylamidinate was used as lithium reagent in 86% yield of the final product. Mass spectrum m/z, theoretical 1009.28; found M + H: 1010.3.
example 14: synthesis of Compound 14
Figure BDA0002862937360000913
Referring to the general synthetic route, lithium NN-diethyl-phenylamidinate was used as lithium reagent in 80% yield of the final product. Mass spectrum m/z, theoretical 958.37; found M + H: 959.37.
example 15: synthesis of Compound 15
Figure BDA0002862937360000914
Referring to the general synthetic route, lithium NN-diisopropyl-phenylamidinate was used as lithium reagent in 81% yield of the final product. Mass spectrum m/z, theoretical 1205.51; found M + H: 1206.5.
example 16: synthesis of Compound 16
Figure BDA0002862937360000921
Referring to the general synthetic route, lithium NN-di-tert-butyl-phenylamidinate was used as lithium reagent in 76% yield of the final product. Mass spectrum m/z, theoretical 1205.52; found M + H: 1206.5.
example 17: synthesis of Compound 17
Figure BDA0002862937360000922
Referring to the general synthetic route, lithium NN-dimethyl-phenylamidinate was used as lithium reagent in 76% yield of the final product. Mass spectrum m/z, theoretical 1141.56; found M + H: 1142.6.
example 18: synthesis of Compound 18
Figure BDA0002862937360000923
Referring to the general synthetic route, lithium NN-diethyl-phenylamidinate was used as lithium reagent in 76% yield of the final product. Mass spectrum m/z, theoretical 1065.54; found M + H: 1066.54.
manufacturing of OLED device:
a P-doped material P-1 to P-5 is evaporated on the surface or anode of ITO/Ag/ITO glass with the size of 2mm multiplied by 2mm in light emitting area or the P-doped material is co-evaporated with the compound in the table with the concentration of 1% to 50% to form a Hole Injection Layer (HIL) with the thickness of 5 nm to 100nm and a Hole Transport Layer (HTL) with the thickness of 5 nm to 200nm, then a light emitting layer (EML) (which can contain the compound) with the thickness of 10 nm to 100nm is formed on the hole transport layer, finally an Electron Transport Layer (ETL) with the thickness of 20 nm to 200nm and a cathode with the thickness of 50 nm to 200nm are formed by the compound in sequence, if necessary, an Electron Blocking Layer (EBL) is added between the HTL and the EML layer, and an Electron Injection Layer (EIL) is added between the ETL and the cathode. The OLEDs were tested by standard methods, as listed in table 1.
To better illustrate the practical gain effects of the present invention, comparative organic electroluminescent elements were prepared using the following commonly used iridium metal complex RD-1 and the iridium metal complexes of the present invention and organic compounds H-1 to H-14 as the main components to illustrate the superiority of the composition of the present invention.
Figure BDA0002862937360000931
In the specific embodiment, the structure of the top-emitting OLED device is on ITO/Ag/ITO-containing glass, HIL is HT-1: P-3(97:3 v/v%), and the thickness is 10 nanometers; HTL is HT-1, and the thickness is 100 nanometers; EBL is HT-8, thickness is 10 nm, EML is the composition of the invention, concretely, (H-1-H-14): (RD-1-RD-6) (97:3 v/v%), thickness is 35 nm, ETL is ET-13: LiQ (50:50 v/v%) with a thickness of 35 nm, then evaporating a cathode Yb of 1 nm, an Ag of 14 nm and an evaporated CPL layer of 70 nm. The characteristics of efficiency, operating voltage, life, etc. according to the above examples and comparative examples are shown in table 1 below.
TABLE 1
Examples EML Driving voltage (volt) Current efficiency (cd/A) LT95 (hours)
Comparison device 1 RD-1:H-1 4.0 40.3 126
Comparison device 2 RD-1:H-4 4.0 40.6 136
Comparison device 3 RD-1:H-5 3.9 42.3 188
Comparison device 4 RD-1:H-9 4.0 41.0 160
Comparison device 5 RD-1:H-14 3.8 42.6 190
Device example 1 Compound 1: H-1 3.9 53.6 138
Device example 2 Compound 2H-1 3.9 51.3 146
Device example 3 Compound 9H-1 3.7 55.8 138
Device example 4 Compound 13H-1 3.8 57.3 150
Device example 5 Compound 17H-1 3.8 57.7 146
Device example 6 Compound 1: H-5 3.7 56.6 213
Device example 7 Compound 2H-5 3.7 54.5 224
Device example 8 Compound 9H-5 3.7 59.8 232
Device example 9 Compound 13H-5 3.7 61.2 218
Device example 10 Compound 17H-5 3.7 61.5 230
Device example 11 Compound 1H-14 3.6 56.0 198
Device example 12 Compound 2H-14 3.6 55.1 214
Device example 13 Compound 9H-14 3.6 58.3 200
Device example 14 Compound 13H-14 3.6 62.0 204
Device example 15 Compound 17H-14 3.6 61.7 210
As can be seen from Table 1, five-membered rings are incorporated into the ligand structure, and the current efficiency of the OLED device can be obviously improved and the driving voltage can be reduced by using the composition provided by the invention under the same conditions from the device 1 to the device example 15 and the comparison devices 1 to 5. Specifically, comparing the device 1 with the device examples 1-5, the combination provided by the invention has obvious advantages. If a new combination is adopted, namely the device examples 6-15 have lower operation voltage, higher luminous efficiency and longer service life compared with the comparison devices 3-5. The composition provided by the invention has remarkable advantages and commercial application value.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (11)

1. A composition is characterized by comprising an iridium metal complex and an organic compound, wherein the structural formula of the iridium metal complex is shown as a formula (I); the structural formula (II) or (III) of the organic compound
Figure FDA0002862937350000011
In formula (I), X is selected from NR1, O, S, CR1R2, SiR1R2, O ═ P-R1 or B-R1; y is selected from N or C-R1; (L ^ Z) is selected from structural formulas represented by the formula (IV),
Figure FDA0002862937350000012
R1-R8 and R11 are independently selected from hydrogen, deuterium, cyano, halogen, C1-C18 alkyl, C1-C18 alkoxy, C1-C18 alkylsilyl, C1-C18 alkoxysilyl, C6-C40 aryl, C1-C40 heteroaryl, substituted or unsubstituted arylether group, substituted or unsubstituted heteroarylether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilicon group, substituted or unsubstituted heteroarylsilicon groupAny one of a group, a substituted or unsubstituted aryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, and a substituted or unsubstituted phosphinyl group; r9, R10 is selected from any one of cyano, C1-C18 alkyl, C1-C18 alkoxy, C6-C40 aryl, C1-C40 heteroaryl, substituted or unsubstituted aryl ether group, substituted or unsubstituted heteroaryl ether group, substituted or unsubstituted aryl acyl, substituted or unsubstituted heteroaryl acyl, and substituted or unsubstituted phosphinyl; all groups may be partially deuterated or fully deuterated. m is taken from 1 or 2, and m + n is 3; heteroaryl means containing B, N, O, S, P (═ O), Si, P at least one heteroatom;
in formula (II) and formula (III), X1 to X6 are CR or N; y1 to Y8 are CR or N, and at least 2 are N; l is absent or selected from single bond, O, S, CRR, SiRR, NR; a and B are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; r is independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, aryl or heteroaryl substituted amine; n is an integer of 0 to 6; adjacent X or Y may form a ring; all groups may be partially deuterated or fully deuterated.
2. The composition as claimed in claim 1, wherein R1 to R11 in the iridium metal complex of formula (I) are selected from one of the following representative structural formulae:
Figure FDA0002862937350000021
3. the composition as claimed in any one of claims 1 to 2, wherein the iridium metal complex of formula (I) is selected from one of the following representative structures:
Figure FDA0002862937350000031
Figure FDA0002862937350000041
Figure FDA0002862937350000051
Figure FDA0002862937350000061
Figure FDA0002862937350000071
Figure FDA0002862937350000081
Figure FDA0002862937350000091
Figure FDA0002862937350000101
Figure FDA0002862937350000111
Figure FDA0002862937350000121
Figure FDA0002862937350000131
Figure FDA0002862937350000141
Figure FDA0002862937350000151
Figure FDA0002862937350000161
Figure FDA0002862937350000171
Figure FDA0002862937350000181
Figure FDA0002862937350000191
Figure FDA0002862937350000201
Figure FDA0002862937350000211
Figure FDA0002862937350000221
Figure FDA0002862937350000231
Figure FDA0002862937350000241
4. the composition of claim 1, wherein formula (II) is selected from the group consisting of compounds of formula II-1 through II-7
Figure FDA0002862937350000251
Wherein X1 to X6, L, A, B, R, n are the same as in claim 1.
5. The composition of claim 1, wherein a and B are selected from the group consisting of those described by the following structures:
Figure FDA0002862937350000252
wherein X1 to X6, Y1 to Y8, L, R, n are the same as in claim 1.
6. The composition according to any one of claims 1 to 5, wherein the organic compound of formula (II) or formula (III) is selected from one of the following representative structures:
Figure FDA0002862937350000261
Figure FDA0002862937350000271
Figure FDA0002862937350000281
Figure FDA0002862937350000291
Figure FDA0002862937350000301
Figure FDA0002862937350000311
Figure FDA0002862937350000321
Figure FDA0002862937350000331
Figure FDA0002862937350000341
Figure FDA0002862937350000351
Figure FDA0002862937350000361
Figure FDA0002862937350000371
Figure FDA0002862937350000381
Figure FDA0002862937350000391
Figure FDA0002862937350000401
Figure FDA0002862937350000411
Figure FDA0002862937350000421
Figure FDA0002862937350000431
Figure FDA0002862937350000441
Figure FDA0002862937350000451
Figure FDA0002862937350000461
Figure FDA0002862937350000471
Figure FDA0002862937350000481
Figure FDA0002862937350000491
Figure FDA0002862937350000501
Figure FDA0002862937350000511
Figure FDA0002862937350000521
Figure FDA0002862937350000531
Figure FDA0002862937350000541
Figure FDA0002862937350000551
Figure FDA0002862937350000561
Figure FDA0002862937350000571
Figure FDA0002862937350000581
Figure FDA0002862937350000591
Figure FDA0002862937350000601
Figure FDA0002862937350000611
Figure FDA0002862937350000621
Figure FDA0002862937350000631
Figure FDA0002862937350000641
Figure FDA0002862937350000651
Figure FDA0002862937350000661
Figure FDA0002862937350000671
Figure FDA0002862937350000681
Figure FDA0002862937350000691
Figure FDA0002862937350000701
Figure FDA0002862937350000711
Figure FDA0002862937350000721
Figure FDA0002862937350000731
Figure FDA0002862937350000741
Figure FDA0002862937350000751
Figure FDA0002862937350000761
Figure FDA0002862937350000771
Figure FDA0002862937350000781
Figure FDA0002862937350000791
Figure FDA0002862937350000801
Figure FDA0002862937350000811
Figure FDA0002862937350000821
Figure FDA0002862937350000831
7. a formulation comprising a composition according to any one of claims 1 to 6 and at least one solvent.
8. A formulation according to claim 7, wherein the composition and the solvent are formulated in the form of a solvent, and the solvent used is not particularly limited, and a halogenated saturated hydrocarbon solvent such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane and the like, a halogenated unsaturated hydrocarbon solvent such as chlorobenzene, dichlorobenzene, trichlorobenzene and the like, an ether solvent such as tetrahydrofuran, tetrahydropyran and the like, an ester solvent such as alkyl benzoate and the like, which are well known to those skilled in the art can be used.
9. An organic electroluminescent device, comprising:
a first electrode;
a second electrode facing the first electrode;
the organic functional layer is clamped between the first electrode and the second electrode;
wherein the light-emitting layer comprises the composition of any one of claims 1 to 6.
10. The organic electroluminescent device according to claim 9, wherein the iridium metal complex and the organic compound are contained in a light-emitting layer, and wherein the iridium metal complex is present in an amount of 1 to 50% by mass.
11. A display or lighting device comprising the organic electroluminescent element according to any one of claims 9 to 10.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150014659A1 (en) * 2013-07-11 2015-01-15 Samsung Display Co., Ltd. Iridium complex and organic light-emitting device including the same
CN108232022A (en) * 2017-12-29 2018-06-29 南京邮电大学 A kind of organic electroluminescence device and preparation method thereof
CN110547049A (en) * 2017-04-27 2019-12-06 住友化学株式会社 Composition and light-emitting element using same
CN110574497A (en) * 2017-04-27 2019-12-13 住友化学株式会社 Composition and light-emitting element using same
CN110574496A (en) * 2017-04-27 2019-12-13 住友化学株式会社 Composition and light-emitting element using same
CN110698387A (en) * 2019-09-04 2020-01-17 宁波卢米蓝新材料有限公司 Fused ring compound and preparation method and application thereof
CN111747991A (en) * 2019-03-29 2020-10-09 三星电子株式会社 Composition and organic light emitting device including the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150014659A1 (en) * 2013-07-11 2015-01-15 Samsung Display Co., Ltd. Iridium complex and organic light-emitting device including the same
CN110547049A (en) * 2017-04-27 2019-12-06 住友化学株式会社 Composition and light-emitting element using same
CN110574497A (en) * 2017-04-27 2019-12-13 住友化学株式会社 Composition and light-emitting element using same
CN110574496A (en) * 2017-04-27 2019-12-13 住友化学株式会社 Composition and light-emitting element using same
CN108232022A (en) * 2017-12-29 2018-06-29 南京邮电大学 A kind of organic electroluminescence device and preparation method thereof
CN111747991A (en) * 2019-03-29 2020-10-09 三星电子株式会社 Composition and organic light emitting device including the same
CN110698387A (en) * 2019-09-04 2020-01-17 宁波卢米蓝新材料有限公司 Fused ring compound and preparation method and application thereof

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