CN114044793A - Organic electrophosphorescent material and application thereof - Google Patents
Organic electrophosphorescent material and application thereof Download PDFInfo
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- CN114044793A CN114044793A CN202111374119.1A CN202111374119A CN114044793A CN 114044793 A CN114044793 A CN 114044793A CN 202111374119 A CN202111374119 A CN 202111374119A CN 114044793 A CN114044793 A CN 114044793A
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- 239000000463 material Substances 0.000 title claims abstract description 134
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 13
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
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- 239000012065 filter cake Substances 0.000 description 6
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- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 2
- AQRDPQOVPUDAQO-UHFFFAOYSA-N n-(2-bromoethyl)aniline Chemical compound BrCCNC1=CC=CC=C1 AQRDPQOVPUDAQO-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 description 1
- IZQAUUVBKYXMET-UHFFFAOYSA-N 2-bromoethanamine Chemical compound NCCBr IZQAUUVBKYXMET-UHFFFAOYSA-N 0.000 description 1
- CJLGKQGYTBDGJZ-UHFFFAOYSA-N 3,7-dimethylnonane-4,6-dione Chemical compound CCC(C)C(=O)CC(=O)C(C)CC CJLGKQGYTBDGJZ-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MJRFDVWKTFJAPF-UHFFFAOYSA-K trichloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)Cl MJRFDVWKTFJAPF-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The application provides an organic electrophosphorescent material and application thereof, wherein the organic electrophosphorescent material comprises a compound shown as a general formula (I) and has a cyclized benzimidazole structure, so that the stability, the modifiability and the film-forming property of the organic electrophosphorescent material are effectively improved. The organic electrophosphorescent material is used as a guest material of a luminescent layer in an organic electroluminescent device, so that the luminous efficiency, stability and luminescent life of the organic electroluminescent device can be effectively improved, and the evaporation energy consumption of the organic electroluminescent device can be effectively reduced. And the organic electrophosphorescent material is more suitable for a hole injection layer, a hole transport layer, an electron injection layer and an electron transport layer in an organic electroluminescent device. The display device provided by the application has an excellent display effect.
Description
Technical Field
The application relates to the field of organic electroluminescent display, in particular to an organic electrophosphorescent material and application thereof.
Background
Compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large visual angle and low power, has the response speed which can reach 1000 times of that of the liquid crystal display, and has the manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
The organic electroluminescent device generally includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode. Wherein the light-emitting layer material comprises a host material and a doped guest material. The stability and film-forming property of the existing phosphorescent material used as a guest material are poor, and the luminous efficiency and stability of an organic electroluminescent device are restricted.
Disclosure of Invention
The embodiment of the application aims to provide an organic electrophosphorescent material which has good stability and film-forming property.
The application provides an organic electrophosphorescent material in a first aspect, which comprises a compound represented by the general formula (I):
wherein the content of the first and second substances,
R1-R12each independently selected from hydrogen, halogen atom, trifluoromethyl, amino, C unsubstituted or substituted by halogen atom1-C5Alkyl radical, C1-C5Heteroalkyl group, C3-C8Alicyclic hydrocarbon group, C6-C12Aryl or C2-C12Heterocyclic aromatic radical, R1-R12Wherein adjacent substituents may be linked to form a ring;
l is a monovalent bidentate ligand, and X and Y are each independently selected from a carbon atom, a nitrogen atom or an oxygen atom;
n is 1, 2 or 3;
the heteroatoms in the heteroalkyl group and the heteroaryl group each independently include an oxygen atom, a sulfur atom, a nitrogen atom.
In a second aspect, the present application provides a use of the organic electrophosphorescent material provided in the first aspect of the present application in an organic electroluminescent device.
In a third aspect, the present application provides an organic electroluminescent device comprising at least one of the organic electrophosphorescent materials provided in the first aspect of the present application.
A fourth aspect of the present application provides a display apparatus comprising an organic electroluminescent device as provided in the third aspect of the present application.
The organic electrophosphorescent material has a cyclized benzimidazole structure, so that the stability, the repairability and the film-forming property of the organic electrophosphorescent material are effectively improved. The organic electrophosphorescent material is used as a guest material of a luminescent layer in an organic electroluminescent device, so that the luminous efficiency, stability and luminescent life of the organic electroluminescent device can be effectively improved, and the evaporation energy consumption of the organic electroluminescent device can be effectively reduced. The organic electrophosphorescent material is used in the luminescent layer, so that the luminescent layer has good matching property with a hole injection layer, a hole transport layer, an electron injection layer and an electron transport layer in an organic electroluminescent device. The display device provided by the application has an excellent display effect.
Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only one embodiment of the present application, and other embodiments can be obtained by those skilled in the art according to the drawings.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The technical solutions in the present application will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in this application are within the scope of protection of this application.
The application provides an organic electrophosphorescent material in a first aspect, which comprises a compound represented by the general formula (I):
wherein the content of the first and second substances,
R1-R12each independently selected from hydrogen, halogen atom, trifluoromethyl, amino, C unsubstituted or substituted by halogen atom1-C5Alkyl radical, C1-C5Heteroalkyl radicals、C3-C8Alicyclic hydrocarbon group, C6-C12Aryl or C2-C12Heterocyclic aromatic radical, R1-R12Wherein adjacent substituents may be linked to form a ring;
l is a monovalent bidentate ligand, and X and Y are each independently selected from a carbon atom, a nitrogen atom or an oxygen atom;
n is 1, 2 or 3;
the heteroatoms in the heteroalkyl group and the heteroaryl group each independently include an oxygen atom, a sulfur atom, a nitrogen atom.
Preferably, R1-R12Each independently selected from hydrogen, halogen atom, trifluoromethyl, amino, C unsubstituted or substituted by halogen atom1-C5Alkyl radical, C1-C5Alkoxy radical, C1-C5Alkylthio radical, C3-C6Alicyclic hydrocarbon group, C6-C12Aryl, pentabasic C2-C12Heterocyclic aromatic radicals or six-membered C2-C12A heterocyclic aromatic group.
More preferably, R1-R12Each independently selected from hydrogen, halogen, trifluoromethyl, phenyl, methyl or ethyl.
In some embodiments of the present application, L is selected from L1 or L2:
R13-R19、R20-R27each independently selected from hydrogen, halogen atom, trifluoromethyl, C1-C4Alkyl radical, C3-C8Alicyclic hydrocarbon group, C6-C12Aryl or C2-C12Heterocyclic aromatic radical, R20-R27Wherein adjacent substituents may be linked to form a ring.
Preferably, R13-R19、R20-R27Each independently selected from hydrogen, halogen, trifluoromethyl, phenyl, methyl, ethyl or isopropyl; r20-R27Each independently selected from hydrogen, halogen, trifluoromethyl, phenyl, methyl or ethyl.
Introduction of L1 or L2 increased the structural area of the compound represented by the general formula (I). Thus, the stability, the modifiability and the film-forming property of the organic electrophosphorescent material are further improved. The organic electrophosphorescent material is used as a guest material of a luminescent layer in the organic electroluminescent device, so that the luminous efficiency, stability and luminescent life of the organic electroluminescent device can be further improved, and the evaporation energy consumption of the organic electroluminescent device can be effectively reduced.
For example, L1 is selected from the following structures:
l2 is selected from the following structures:
in some embodiments of the present application, the organic electrophosphorescent material comprises a compound of formula (I-A), a compound of formula (I-B), or a compound of formula (I-C):
preferably, the compound of formula (I-A) includes any one of the following compounds A-1 to A-18:
more preferably, the compound of formula (I-A) includes any one of the following compounds A-1 to A-9:
preferably, the compound of formula (I-B) includes any one of the following compounds B-1 to B-18:
more preferably, the compound of formula (I-B) includes any one of the following compounds B-1 to B-9:
preferably, the compound of formula (I-C) includes any one of the following compounds C-1 to C-18:
more preferably, the compound of formula (I-C) includes any one of the following compounds C-1 to C-9:
the compound shown in the general formula (I) is a metal iridium complex with cyclized benzimidazole, has a rigid group (such as a nitrogen-oxygen seven-membered heterocycle and benzimidazole) or forms a cyclic structure between C-N bonds, can reduce the possibility of high-temperature chain scission of the C-N bonds, improves the stability of an organic phosphorescent material, and effectively reduces the agglomeration effect of the organic phosphorescent material in the evaporation process. The structure of the compound shown in the general formula (I) is easy to modify, the emission wavelength of the organic phosphorescent material can be changed by adding a rigid group, and the quantum efficiency and the luminescence property are improved.
The organic electrophosphorescent material provided by the first aspect of the application comprises a compound shown as a general formula (I) and has a cyclized benzimidazole structure, so that the stability, the modifiability and the film-forming property of the organic electrophosphorescent material are effectively improved.
In a second aspect, the present application provides a use of the organic electrophosphorescent material provided in the first aspect of the present application in an organic electroluminescent device. The organic electrophosphorescent material provided by the first aspect of the application is used in an organic electroluminescent device, so that the stability and the luminous efficiency of the organic electroluminescent device can be improved, and the organic electrophosphorescent material is used in a luminous layer, so that the luminous layer and a hole injection layer, a hole transport layer, an electron injection layer and an electron transport layer in the organic electroluminescent device have good matching property.
In a third aspect, the present application provides an organic electroluminescent device comprising at least one of the organic electrophosphorescent materials provided in the first aspect of the present application.
Further, the organic electrophosphorescent material is used as a guest material of the light-emitting layer.
In the present application, there is no particular limitation on the kind and structure of the organic electroluminescent device, and there may be various types and structures of organic electroluminescent devices known in the art as long as at least one of the guest materials of the light-emitting layer provided herein may be used.
The organic electroluminescent device of the present application may be a light-emitting device having a top emission structure, and examples thereof include a structure comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a bottom emission structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially provided on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a double-sided light-emitting structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode are sequentially provided on a substrate.
In addition, the organic electroluminescent device may further have an electron blocking layer between the hole transport layer and the light emitting layer, and/or a hole blocking layer between the light emitting layer and the electron transport layer, and/or a light extraction layer on the transparent cathode on the light emitting side. However, the structure of the organic electroluminescent device of the present application is not limited to the above-described specific structure, and those skilled in the art may omit or add the above-described layers according to actual needs. For example, the organic electroluminescent device may include an anode (10nm to 1000nm), a hole injection layer (5nm to 20nm), a hole transport layer (30nm to 80nm), a light emitting layer (10nm to 50nm), an electron transport layer (20nm to 50nm), an electron injection layer (0.5nm to 10nm), and a transparent or translucent cathode (10nm to 20nm) in this order on a substrate.
Fig. 1 shows a schematic diagram of a typical organic electroluminescent device, in which a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8 are sequentially disposed from bottom to top.
It is to be understood that fig. 1 schematically shows the structure of a typical organic electroluminescent device, and the present application is not limited to this structure, and the guest material of the light emitting layer of the present application may be used in any type of organic electroluminescent device. For example, the organic electroluminescent device may further include an electron blocking layer, a hole blocking layer, a light extraction layer, etc., and these layers may be added or omitted as the case may be, in practical use.
For convenience, the organic electroluminescent device of the present application is described below with reference to fig. 1, but this is not meant to limit the scope of the present application in any way. It is understood that all organic electroluminescent devices capable of using the emissive layer guest materials of the present application are within the scope of the present application.
In the present application, the material of the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, for example, glass with Thin Film Transistor (TFT) components, polymer materials, and the like, may be used.
In the present application, the material of the anode 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) known in the art2) The transparent conductive material such as zinc oxide (ZnO) or Low Temperature Polysilicon (LTPS) may be selected from metal materials such as silver and its alloy, aluminum and its alloy, organic conductive materials such as poly (3, 4-ethylenedioxythiophene) (PEDOT), and a multilayer structure of the above materials.
In the present application, the material of the hole injection layer 3 is not particularly limited, and a hole injection material known in the art may be used. For example, the known hole injection material may be selected from, but is not limited to, at least one of the following compounds HI-1(HAT-CN) to HI-3:
in the present application, the hole injection layer 3 may further include a p-type dopant, the kind of which is not particularly limited, and various p-type dopants known in the art may be used, for example, the p-type dopant may be selected from at least one of the following compounds p-1 to p-2:
in the present application, the amount of the p-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the material of the hole transport layer 4 is not particularly limited, and a hole transport material known in the art may be used. For example, known hole transport materials may be selected from, but are not limited to, at least one of the following compounds HT-1 to HT-31:
in the present application, the material of the light-emitting layer 5 includes a light-emitting layer material including a light-emitting layer host material and a light-emitting layer guest material.
The amount of the host material for the light-emitting layer used in the present application is not particularly limited, and may be an amount known to those skilled in the art. The present application does not specifically limit the kind of the host material of the light-emitting layer as long as the object of the present application can be achieved. For example, the light emitting layer host material may be selected from, but is not limited to, at least one of the following compounds GPH-1 to GPH-30:
in the present application, the guest material of the light-emitting layer may include at least one of the organic electrophosphorescent materials of the present application, or may include a combination of at least one of the organic electrophosphorescent materials of the present application and at least one of the following known guest materials of the light-emitting layer.
For example, known light-emitting layer guest materials may be selected from, but are not limited to, at least one of the following compounds GD01 to GD 04:
in some embodiments of the present application, the mass concentration ρ of the organic electrophosphorescent material in the material of the light-emitting layer i5% -15%, preferably, the mass concentration rho of the organic electrophosphorescent material in the luminescent layer material i8 to 10 percent. Mass concentration rho of organic electrophosphorescent material in luminescent layer materialiThe regulation and control within the range are more beneficial to the improvement of the luminous efficiency of the organic electroluminescent device. When the mass concentration of the organic electrophosphorescent material in the luminescent layer material is controlled in a preferred range, the luminescent efficiency of the organic electroluminescent device is higher. The term "light-emitting layer material" refers to a material including both a light-emitting layer host material and a light-emitting layer guest material.
In the present application, the material of the electron transport layer 6 is not particularly limited, and electron transport materials known in the art may be used. For example, known electron transport materials may be selected from, but are not limited to, at least one of the following ET-1 to ET-37 compounds:
in the present application, the electron transport layer 6 may further include an n-type dopant, the kind of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
in the present application, the amount of the n-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and for example, may include, but are not limited to, LiQ, LiF, NaCl, CsF, Li in the prior art2O、Cs2CO3At least one of BaO, Na, Li, Ca and the like.
In the present application, the material of the cathode 8 is not particularly limited, and may be selected from, but not limited to, magnesium-silver mixture, magnesium-aluminum mixture, metal such as LiF/Al, ITO, Al, etc., metal mixture, oxide, etc.
A fourth aspect of the present application provides a display device comprising the organic electroluminescent device provided by the third aspect of the present application, having an excellent display effect. The display device includes, but is not limited to, a display, a television, a mobile communication terminal, a tablet computer, and the like.
The method for manufacturing the organic electroluminescent device is not particularly limited, and any method known in the art may be used, for example, the method for manufacturing the organic electroluminescent device may include, but is not limited to, the following steps:
(1) cleaning an anode 2 on an organic electroluminescent device substrate 1 for top emission, respectively carrying out steps of medicinal washing, water washing, hairbrush, high-pressure water washing, air knife and the like in a cleaning machine, and then carrying out heat treatment;
(2) vacuum evaporating a hole injection material on the anode 2 to form a hole injection layer 3;
(3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;
(4) vacuum evaporating a main material of a light-emitting layer on the hole transport layer 4, and then vacuum evaporating a material of the light-emitting layer on the main material of the light-emitting layer, wherein the material of the light-emitting layer comprises the main material of the light-emitting layer and the organic electrophosphorescent material of the application, and the mass concentration rho of the organic electrophosphorescent material in the material of the light-emitting layer i5% -15%;
(5) vacuum evaporating an electron transport material on the luminescent layer 5 to form an electron transport layer 6;
(6) vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;
(7) a cathode material is vacuum-deposited on the electron injection layer 7 as a cathode 8.
The above description has been made only of the structure of a typical organic electroluminescent device and a method for manufacturing the same, and it should be understood that the present application is not limited to this structure. The guest material of the light-emitting layer of the present application may be used in an organic electroluminescent device of any structure, and the organic electroluminescent device may be manufactured using any manufacturing method known in the art.
The method for synthesizing the compound of the present application is not particularly limited, and the compound can be synthesized by a method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
Synthesis of Main ligand M1
In a 2L three-necked flask with mechanical stirring, 21.89g of 1-bromo-2-fluoro-3-nitrobenzene (0.1mol), 22.19g of 2-bromoethylaniline (0.12mol), 0.36g of tris (dibenzylideneacetone) dipalladium (Pd) were added in this order2(dba)3) (0.0004mol), 0.08g of tri-tert-butylphosphine (0.0004mol), 21.69g of sodium tert-butoxide (0.226mol) and 1.7L of toluene, mechanical stirring being switched on. Replacement of Nitrogen (N)2) In N at2Raising the temperature to 80 ℃ under protection and preserving the heat for 1 h. After the reaction is finished, 30.71g of brown solid P1 is obtained after separation, extraction, drying, chromatography and drying, and the yield is 80%.
38.39g of P1(0.1mol) and 31.6g of Na were added in this order to a 2L three-necked flask with mechanical stirring2S (0.4mol), 300ml ethanol (EtOH), 100ml H2O, in N2And (5) refluxing and reacting for 2h under protection, and finishing the reaction. 27.6g of white solid P2 is obtained after separation, extraction, drying, chromatography column passing and drying, and the yield is 78%.
35.39g of P2(0.1mol), 300ml of acetone, 11.2g of potassium hydroxide (0.2mol) and 50ml of water are sequentially added into a 2L three-necked flask with mechanical stirring, 44g of benzoyl chloride (0.3mol) is slowly added into the mixture, and the mixture is reacted for 2 hours at normal temperature to obtain a crude product. After separation, extraction, drying, chromatography column chromatography and drying, 38.92g of white solid P3 is obtained with 85% yield.
In a 2L three-necked flask with mechanical stirring, 45.79g of P3(0.1mol) and 300ml of diethylene glycol ether (DEG) were added in this order. N is a radical of2And (5) refluxing and reacting for 2h under protection, and finishing the reaction. After separation, extraction, drying, chromatography column chromatography and drying, 36.08g of white solid P4 is obtained with the yield of 82%.
44g of P4(0.1mol), 700ml of Tetrahydrofuran (THF) and liquid nitrogen are sequentially added into a 2L three-necked flask with mechanical stirring, the temperature is reduced to below 70 ℃, 100ml of n-butyllithium (n-BuLi) (2.5mol) is slowly dripped, and the temperature is kept for 2h after the dripping is finished, so that P5 is obtained. 200ml of DEG and 31g of benzenesulfonic acid (0.2mol) are added, the temperature is raised to 150 ℃ for reaction for 3 hours, and then the mixture is separated, extracted, dried, passed through a chromatographic column and dried to obtain 25.03g of white solid M1 with the yield of 84%.
Ion mass to charge ratio (MS) of M1 (M/e): 298; elemental analysis (C)20H14N2O): theoretical value: c: 80.52%, H: 4.73%, N: 9.39 percent; found value C: 80.12%, H: 4.82%, N: 9.25 percent.
Synthesis of Main ligand M2
Into a 2L three-necked flask with mechanical stirring were successively charged 29.61g of 2-bromo-3-fluoro-1-phenyl-4-nitrobenzene (0.1mol), 22.19g of 2-bromoethylamine (0.12mol), and 0.36g of Pd2(dba)3(0.0004mol), 0.08g of tri-tert-butylphosphine (0.0004mol), 21.69g of sodium tert-butoxide (0.226mol) and 1.7L of toluene, mechanical stirring being switched on. Substitution of N2In N at2Raising the temperature to 80 ℃ under protection and preserving the heat for 1 h. After the reaction is finished, 39.09g of brown solid Q1 is obtained after separation, extraction, drying, chromatography and drying, and the yield is 85%.
Into a 2L three-necked flask with mechanical stirring were charged 45.99g of Q1(0.1mol) and 31.6g of Na in this order2S (0.4mol), 300ml of EtOH, 100ml of H2O, in N2And (5) refluxing and reacting for 2h under protection, and finishing the reaction. After separation, extraction, drying, chromatography column chromatography and drying, 34.56g of white solid Q2 is obtained with the yield of 80%.
43.21g of Q2(0.1mol), 300ml of acetone, 11.2g of potassium hydroxide (0.2mol) and 50ml of water are sequentially added into a 2L three-necked flask with mechanical stirring, 44g of benzoyl chloride (0.3mol) is slowly added, and the reaction is carried out at normal temperature for 2 hours to obtain a crude product. After separation, extraction, drying, chromatography column chromatography and drying, 45.58g of white solid Q3 is obtained with 85% yield.
In a 2L three-necked flask with mechanical stirring, 53.63g of Q3(0.1mol) and 300ml of DEG were sequentially added. N is a radical of2And (5) refluxing and reacting for 2h under protection, and finishing the reaction. After separation, extraction, drying, chromatography column chromatography and drying, 40.93g of white solid Q4 is obtained with the yield of 79%.
51.82g of Q4(0.1mol), 700ml of THF and liquid nitrogen are sequentially added into a 2L three-mouth bottle with mechanical stirring, the temperature is reduced to below 70 ℃, 100ml of n-BuLi (2.5mol) is slowly dripped, and the temperature is kept for 2h after the dripping is finished to obtain Q5. 200ml of DEG and 31g of benzenesulfonic acid (0.2mol) are added, the temperature is raised to 150 ℃ for reaction for 3 hours, and then the mixture is separated, extracted, dried, passed through a chromatographic column and dried to obtain 30.32g of white solid M2 with the yield of 81%.
MS (M/e) of M2: 374; elemental analysis (C)26H18N2O): theoretical value: c: 83.40%, H: 4.85%, N: 7.48 percent; found value C: 82.12%, H: 4.82%, N: 7.25 percent.
Synthesis of Main ligand M3
Into a 2L three-necked flask with mechanical stirring were charged 29.61g of 2-bromo-3-fluoro-4-nitrobenzene (0.1mol), 22.19g of 2-bromoethylaniline (0.12mol), and 0.36g of Pd in that order2(dba)3(0.0004mol), 0.08g of tritertineButylphosphine (0.0004mol), 21.69g sodium tert-butoxide (0.226mol) and 1.7L toluene, mechanical stirring being switched on. Substitution of N2In N at2Raising the temperature to 80 ℃ under protection and preserving the heat for 1 h. After the reaction is finished, 39.09g of brown solid Q1 is obtained after separation, extraction, drying, chromatography and drying, and the yield is 85%.
Into a 2L three-necked flask with mechanical stirring were charged 45.99g of Q1(0.1mol) and 31.6g of Na in this order2S (0.4mol), 300ml of EtOH, 100ml of H2O, in N2And (5) refluxing and reacting for 2h under protection, and finishing the reaction. After separation, extraction, drying, chromatography column chromatography and drying, 34.56g of white solid Q2 is obtained with the yield of 80%.
43.21g of Q2(0.1mol), 300ml of acetone, 11.2g of potassium hydroxide (0.2mol) and 50ml of water are sequentially added into a 2L three-necked flask with mechanical stirring, 66.8g of 3-cyclohexane-1-benzoyl chloride (0.3mol) is slowly added into the mixture, and the mixture is reacted for 2 hours at normal temperature to obtain a crude product. After separation, extraction, drying, chromatography column chromatography and drying, 42.22g of white solid F3 is obtained with the yield of 78%.
In a 2L three-necked flask with mechanical stirring, 54.20g of F3(0.1mol) and 300ml of DEG were sequentially added. N is a radical of2And (5) refluxing and reacting for 2h under protection, and finishing the reaction. After separation, extraction, drying, chromatography column chromatography and drying, 41.39g of white solid F4 is obtained with the yield of 79%.
52.40g of F4(0.1mol), 700ml of THF and liquid nitrogen are sequentially added into a 2L three-mouth bottle with mechanical stirring, the temperature is reduced to below 70 ℃, 100ml of n-BuLi (2.5mol) is slowly dripped, and the temperature is kept for 2h after the dripping is finished to obtain F5. 200ml of DEG and 31g of benzenesulfonic acid (0.2mol) are added, the temperature is raised to 150 ℃ for reaction for 3 hours, and then 32.31g of white solid M3 is obtained after separation, extraction, drying, chromatography and drying, and the yield is 85%.
MS (M/e) of M3: 380 of the raw material; elemental analysis (C)26H24N2O): theoretical value: c: 82.07%, H: 6.36%, N: 7.36 percent; found value C: 82.22%, H: 6.82%, N: 7.25 percent.
Synthetic examples
Synthesis example 1: synthesis of Compound A-1
Into a 250ml three-necked flask, 4.9g of iridium acetylacetonate (Ir (acac)3) (0.01mol), 14.9g of Main ligand M1(0.05mol), glycerol 100ml, N2Stirring is started under protection. Refluxing for 12h at 180 ℃ to obtain a product, and filtering, extracting and passing through a chromatographic column to obtain a yellow solid A-1, namely the compound A-1 with the yield of 75%.
MS (m/e) of Compound A-1: 1084. elemental analysis: (C)60H39IrN6O3) Calculated value (mass fraction/%): c: 66.47, H: 3.63, N: 7.75; found value (mass fraction/%) C: 60.05, H: 3.85, N: 6.20.
synthesis example 2: synthesis of Compound B-1
In N2Under protection, a 5L three-neck flask was placed in an oil bath. 14.9g of the master ligand M1(0.05mol) and 1.5L of DEG, 50ml of water were added thereto and stirred. Substitution of N2Thereafter, 7.05g of iridium trichloride monohydrate (IrCl) was charged into a 5L three-necked flask3·H2O) (0.02mol), heating the reaction system to 150 ℃, and carrying out reflux reaction for 24 hours, wherein when yellow solid is generated in the reaction system, the reaction is stopped. And cooling the system to room temperature, and performing suction filtration to obtain an orange solid. The filter cake is firstly leached by 80ml DEG, then the obtained solid is naturally dried after 40ml ethanol is used for leaching, 27.95g of yellow solid is obtained, namely the compound Q1, and the yield is 85%.
Elemental analysis: (C)80H52Cl2Ir2N8O4) Calculated value (mass fraction/%): c: 58.42, H: 3.19, N: 6.81; found value (mass fraction/%) C: 57.36, H: 3.55, N: 6.20.
in N2Under protection, 1.5g of acetylacetone (0.015mol) and 2.55g of Na were added to a 250ml three-necked flask2CO3(0.024mol) and 50ml DEG. N is a radical of2After the substitution, 4.93g of Q1(0.003mol) was added to the system. The system was heated to 150 ℃ and the reaction refluxed for 27h in the dark. And cooling the system to room temperature, carrying out suction filtration, leaching a filter cake with 100ml of deionized water, and leaching with 100ml of DEG, 100ml of ethanol and 100ml of heptane respectively to obtain a yellow-green solid. Naturally drying to obtain 4.47g of yellow green solid, namely the compound B-1, with the yield of 85 percent.
MS (m/e) of Compound B-1: 886. elemental analysis: (C)45H33IrN4O4) Calculated value (mass fraction/%): c: 61.00, H: 3.75, N: 6.32; found value (mass fraction/%) C: 60.05, H: 3.85, N: 6.20.
synthetic example 3: synthesis of Compound B-3
In N2Under protection, a 5L three-neck flask was placed in an oil bath. 18.7g of the master ligand M2(0.05mol) and 1.5L of DEG, 50ml of H2O is added into the mixture and stirred. Substitution of N2Thereafter, 7.05g of IrCl was added to a 5L three-necked flask3·H2And O (0.02mol), heating the reaction system to 150 ℃, and carrying out reflux reaction for 24 hours, wherein when yellow solid is generated in the reaction system, the reaction is stopped. And cooling the system to room temperature, and performing suction filtration to obtain an orange solid. The filter cake is firstly leached by 80ml of DEG, then the obtained solid is naturally dried after 40ml of ethanol is washed, 19.48g of yellow solid is obtained, namely the compound S1, and the yield is 80%.
Elemental analysis: (C)104H68Cl2Ir2N8O4) Calculated value (mass fraction/%): c: 64.09, H: 3.52, N: 5.75; found value (mass fraction/%) C: 63.36, H: 3.15, N: 5.40.
in N22.32g of 2, 6-dimethyl-3, 5-heptanedione (0.015mol) and 2.55g of Na were added to a 250ml three-necked flask under protection2CO3(0.024mol) and 50ml DEG. N is a radical of2After the substitution, 5.85g of S1(0.003mol) was added to the system. Adding intoThe reaction was heated to 150 ℃ and refluxed for 27h in the dark. And cooling the system to room temperature, carrying out suction filtration, leaching a filter cake with 100ml of deionized water, and leaching with 100ml of DEG, 100ml of ethanol and 100ml of heptane respectively to obtain a yellow-green solid. Naturally drying to obtain 1.35g of yellow-green solid, namely the compound B-3, with the yield of 82%.
MS (m/e) of Compound B-3: 886. elemental analysis: (C)61H49IrN4O4) Calculated value (mass fraction/%): c: 66.95, H: 4.51, N: 5.12; found value (mass fraction/%) C: 67.05, H: 4.55, N: 5.20.
synthetic example 4: synthesis of Compound B-6
In N2Under protection, a 5L three-neck flask was placed in an oil bath. 18.7g of the master ligand M3(0.05mol) and 1.5L of DEG, 50ml of H2O is added into the mixture and stirred. Substitution of N2Thereafter, 7.05g of IrCl was added to a 5L three-necked flask3·H2And O (0.02mol), heating the reaction system to 150 ℃, and carrying out reflux reaction for 24 hours, wherein when yellow solid is generated in the reaction system, the reaction is stopped. And cooling the system to room temperature, and performing suction filtration to obtain an orange solid. The filter cake is firstly leached by 80ml of DEG, then the obtained solid is naturally dried after 40ml of ethanol is washed, and 20.02g of yellow solid is obtained, namely the compound S2, with the yield of 83%.
Elemental analysis: (C)104H68Cl2Ir2N8O4) Calculated value (mass fraction/%): c: 64.09, H: 3.52, N: 5.75; found value (mass fraction/%) C: 64.36, H: 3.25, N: 5.36.
in N2To a 250ml three-necked flask, 2.76g of 3, 7-dimethyl-4, 6-nonanedione (0.015mol) and 2.55g of Na were added under protection2CO3(0.024mol) and 50ml DEG. N is a radical of2After the substitution, 5.85g of S2(0.003mol) was added to the system. The system was heated to 150 ℃ and the reaction refluxed for 27h in the dark. Cooling the system to room temperature, suction-filtering, using 100ml of filter cakeEluting with deionized water, and eluting with 100ml DEG, 100ml ethanol and 100ml heptane respectively to obtain yellow-green solid. Naturally drying to obtain 1.43g of yellow-green solid, namely the compound B-6, with the yield of 85 percent.
MS (m/e) of Compound B-6: 886. elemental analysis: (C)63H53IrN4O4) Calculated value (mass fraction/%): c: 67.42, H: 4.76, N: 4.99; found value (mass fraction/%) C: 67.05, H: 4.35, N: 5.12.
synthesis example 5: synthesis of Compound C-1
In N2Under protection, a 5L three-neck flask was placed in an oil bath. 14.9g of the master ligand M1(0.05mol) and 1.5L of DEG, 50ml of water were added thereto and stirred. Substitution of N2Thereafter, 7.05g of IrCl was added to a 5L three-necked flask3·H2And O (0.02mol), heating the reaction system to 150 ℃, and carrying out reflux reaction for 24 hours, wherein when yellow solid is generated in the reaction system, the reaction is stopped. And cooling the system to room temperature, and performing suction filtration to obtain an orange solid. The filter cake is firstly leached by 80ml of DEG, and then the obtained solid is naturally dried after being rinsed by 40ml of ethanol, so that 27.95g of yellow solid, namely the compound Q1 is obtained, and the yield is 85%.
Elemental analysis: (C)80H52Cl2Ir2N8O4) Calculated value (mass fraction/%): c: 58.42, H: 3.19, N: 6.81; found value (mass fraction/%) C: 57.36, H: 3.55, N: 6.20.
in N22.34g of 2-phenylpyridine (0.015mol) and 2.55g of Na were added to a 250ml three-necked flask under protection2CO3(0.024mol) and 50ml of Dimethylformamide (DMF). N is a radical of2After the substitution, 4.93g of Q1(0.003mol) was added to the system. The system was heated to 120 ℃ and the reaction was refluxed for 24h in the dark. Cooling the system to room temperature, filtering, decompressing, spin-drying the solvent, and separating and purifying the target product by using a chromatographic column (dichloromethane: methanol) to obtain a yellow-green solid. After naturally drying4.91g of yellow-green solid is obtained, namely the compound C-1, and the yield is 86%.
MS (m/e) of Compound C-1: 941. elemental analysis: (C)51H34IrN5O2) Calculated value (mass fraction/%): c: 65.09, H: 3.64, N: 7.44; found value (mass fraction/%) C: 64.05, H: 3.55, N: 7.20.
example 1
Ultrasonically treating the glass plate coated with the ITO transparent conductive layer with the thickness of 130nm in a HELLMA washing solution for 90min, washing in deionized water, preserving heat for 1h at 120 ℃ in a ventilated oven, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
then, the glass substrate with the anode is placed in a vacuum chamber and is vacuumized to be less than 10 DEG-5In the torr, vacuum evaporating a hole injection material HI-1 on the anode layer film to be used as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 15 nm;
then, vacuum evaporating a hole transport material HT-31 on the hole injection layer to be used as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 50 nm;
then, vacuum evaporating a light-emitting layer main body material GPH-30 on the hole transport layer to form a film layer with the thickness of 5nm, and then vacuum evaporating a light-emitting layer material on the film layer to form a film layer with the thickness of 15nm, namely obtaining a light-emitting layer with the thickness of 20 nm; the light-emitting layer material comprises a light-emitting layer host material GPH-30 and a light-emitting layer guest material A-1 with the mass concentration of 8%, evaporation is carried out by using a multi-source co-evaporation method, the evaporation rate of the light-emitting layer host material GPH-30 is adjusted to be 0.1nm/s, and the evaporation rate of the light-emitting layer guest material A-1 is 4% of the evaporation rate of the light-emitting layer host material GPH-30;
then, vacuum evaporation is carried out on the electron transport material ET-37 on the luminescent layer to be used as an electron transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 35 nm;
then, vacuum evaporation is carried out on the electron transport layer to obtain an electron injection material LiF as an electron injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 1 nm;
then, an Al layer is vacuum-evaporated on the electron injection layer as a cathode of the organic electroluminescent device, wherein the evaporation rate is 1nm/s, and the evaporation film thickness is 80 nm.
Examples 2 to 5
The procedure of example 1 was repeated, except that the guest materials of the light-emitting layer were replaced with the compounds B-1, B-3, B-6 and C-1.
Examples 6 to 8
Except that the mass concentration ρ of the guest material of the light-emitting layer in the material of the light-emitting layer was adjusted in accordance with Table 1iOtherwise, the same procedure as in example 2 was repeated.
Comparative example 1
The same as example 1 except that the light-emitting layer guest material was replaced with the compound GD 01.
Comparative examples 2 to 3
Except that the mass concentration ρ of the guest material of the light-emitting layer in the material of the light-emitting layer was adjusted in accordance with Table 1iOtherwise, the same procedure as in example 2 was repeated.
The organic electroluminescent devices obtained in examples 1 to 8 and comparative examples 1 to 3 were subjected to the following performance tests:
(1) testing of starting voltage, current density and brightness:
the starting voltage and current density of the organic electroluminescent devices prepared in each example and each comparative example were measured using a digital source meter and a luminance meter, and specifically, the maximum luminance data of the organic electroluminescent devices at the starting voltage of 0V to 5V was measured at a rate of 0.1V per second, and the current density at that time was measured.
(2) Testing of External Quantum Efficiency (EQE):
EQE of each example and each comparative organic electroluminescent device prepared was measured using an Electroluminescent (EL) spectrum measuring instrument (manufacturer: F-Star, model: PR 670).
(3) Test of current luminous efficiency (CE), test of power luminous efficiency (PE), test of color Coordinates (CIE):
an electrochemical working platform for testing the photoelectric properties of the organic electroluminescent device was used, a digital ammeter (manufacturer: Keithley, model: 2400) supplied with a voltage, and a light dispersion meter (manufacturer: Topcon, model: SR-UL1R) for receiving light emitted from the device. In the testing process, an initial voltage of 10V and a spacing voltage of 0.1V are set on a computer testing software for a digital electric meter, a forward voltage is given by an electrode of an external organic electroluminescent device of the digital electric meter, light emitted by the organic electroluminescent device corresponding to each voltage value is analyzed by a light splitting radiancy meter, the color coordinate of the light is analyzed, and finally, the computer outputs data to test CE, PE and CIE of the organic electroluminescent device.
(4) Testing of wavelength:
the wavelengths obtained in each example and each comparative preparation were measured using an EL spectrometer (manufacturer: F-Star, model: PR 670).
The test results for each example and each comparative example are shown in table 1.
Table 1 organic electroluminescent device performance test results
As can be seen from examples 1-5 and comparative example 1, the compounds A-1, B-3, B-6 and C-1 provided by the application are selected as guest materials of a light-emitting layer to be applied to the light-emitting layer, and the prepared organic electroluminescent device has higher current density, brightness, external quantum efficiency, current luminous efficiency and power luminous efficiency. The organic electrophosphorescent material is used as a guest material of a luminescent layer in an organic electroluminescent device, so that the luminous efficiency of the organic electroluminescent device can be effectively improved.
As can be seen from examples 2,6 to 8 and comparative examples 2 to 3, the luminous efficiency of the organic electroluminescent device is dependent on the mass concentration ρ of the organic electrophosphorescent material in the material of the light-emitting layeriMay vary. Selecting mass concentration rhoiIn the context of the present applicationThe organic electroluminescent device in the enclosure has obviously better luminous efficiency.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (15)
1. An organic electrophosphorescent material comprising a compound represented by the general formula (I):
wherein the content of the first and second substances,
R1-R12each independently selected from hydrogen, halogen atom, trifluoromethyl, amino, C unsubstituted or substituted by halogen atom1-C5Alkyl radical, C1-C5Heteroalkyl group, C3-C8Alicyclic hydrocarbon group, C6-C12Aryl or C2-C12Heterocyclic aromatic radical, R1-R12Wherein adjacent substituents may be linked to form a ring;
l is a monovalent bidentate ligand, and X and Y are each independently selected from a carbon atom, a nitrogen atom or an oxygen atom;
n is 1, 2 or 3;
the heteroatoms in the heteroalkyl group and the heteroaryl group each independently include an oxygen atom, a sulfur atom, a nitrogen atom.
2. The organic electrophosphorescent material of claim 1, wherein R is1-R12Each independently selected from hydrogen, halogen atom, trifluoromethyl, amino, C unsubstituted or substituted by halogen atom1-C5Alkyl radical, C1-C5Alkoxy radical, C1-C5Alkylthio radical, C3-C6Alicyclic hydrocarbon group, C6-C12Aryl, pentabasic C2-C12Heterocyclic aromatic radicals or six-membered C2-C12A heterocyclic aromatic group.
3. The organic electrophosphorescent material of claim 2, wherein R is1-R12Each independently selected from hydrogen, halogen, trifluoromethyl, phenyl, methyl or ethyl.
4. The organic electrophosphorescent material of claim 1, wherein L is selected from the following L1 or L2:
R13-R19、R20-R27each independently selected from hydrogen, halogen atom, trifluoromethyl, C1-C4Alkyl radical, C3-C8Alicyclic hydrocarbon group, C6-C12Aryl or C2-C12Heterocyclic aromatic radical, R20-R27Wherein adjacent substituents may be linked to form a ring.
5. The organic electrophosphorescent material of claim 4, wherein R is13-R19、R20-R27Each independently selected from hydrogen, halogen, trifluoromethyl, phenyl, methyl, ethyl or isopropyl;
R20-R27each independently selected from hydrogen, halogen, trifluoromethyl, phenyl, methyl or ethyl.
6. The organic electrophosphorescent material of claim 4, wherein L1 is selected from the following structures:
l2 is selected from the following structures:
7. the organic electrophosphorescent material of claim 4, comprising a compound of formula (I-A), a compound of formula (I-B), or a compound of formula (I-C):
8. the organic electrophosphorescent material of claim 7, wherein the compound of formula (I-a) comprises any one of the following compounds a-1 to a-18:
the compound of the formula (I-B) includes any one of the following compounds B-1 to B-18:
the compound of formula (I-C) includes any one of the following compounds C-1 to C-18:
9. the organic electrophosphorescent material of claim 7, wherein the compound of formula (I-a) comprises any one of the following compounds a-1 to a-9:
the compound of the formula (I-B) includes any one of the following compounds B-1 to B-9:
the compound of formula (I-C) includes any one of the following compounds C-1 to C-9:
10. use of the organic electrophosphorescent material of any one of claims 1 to 9 in an organic electroluminescent device.
11. An organic electroluminescent device comprising at least one of the organic electrophosphorescent materials of any one of claims 1 to 9.
12. The organic electroluminescent device according to claim 11, wherein the organic electrophosphorescent material is used as a guest material of an emission layer.
13. The organic electroluminescent device according to claim 11 or 12, wherein the mass concentration p of the organic electrophosphorescent material in the light emitting layer materiali5 to 15 percent.
14. The organic electroluminescent device according to claim 11 or 12, wherein the mass concentration p of the organic electrophosphorescent material in the light emitting layer materiali8 to 10 percent.
15. A display device comprising the organic electroluminescent device according to any one of claims 11 to 14.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726606A (en) * | 2002-11-08 | 2006-01-25 | 通用显示公司 | Organic light emitting materials and devices |
| US20170040552A1 (en) * | 2015-08-03 | 2017-02-09 | Universal Display Corporation | Organic Electroluminescent Materials and Devices |
| CN112209973A (en) * | 2020-11-05 | 2021-01-12 | 北京燕化集联光电技术有限公司 | O-containing organic electrophosphorescent material and application thereof |
| CN112625066A (en) * | 2019-10-08 | 2021-04-09 | 环球展览公司 | Organic electroluminescent material and device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726606A (en) * | 2002-11-08 | 2006-01-25 | 通用显示公司 | Organic light emitting materials and devices |
| US20170040552A1 (en) * | 2015-08-03 | 2017-02-09 | Universal Display Corporation | Organic Electroluminescent Materials and Devices |
| CN112625066A (en) * | 2019-10-08 | 2021-04-09 | 环球展览公司 | Organic electroluminescent material and device |
| CN112209973A (en) * | 2020-11-05 | 2021-01-12 | 北京燕化集联光电技术有限公司 | O-containing organic electrophosphorescent material and application thereof |
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