CN112028879B - Electron transport material, organic electroluminescent device and display device - Google Patents
Electron transport material, organic electroluminescent device and display device Download PDFInfo
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- CN112028879B CN112028879B CN202011052902.1A CN202011052902A CN112028879B CN 112028879 B CN112028879 B CN 112028879B CN 202011052902 A CN202011052902 A CN 202011052902A CN 112028879 B CN112028879 B CN 112028879B
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- organic electroluminescent
- electron transport
- electroluminescent device
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting 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
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- 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
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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Abstract
The invention discloses an electron transport material of general formula I, which can be used as an electron transport layer of an organic electroluminescent device in a display device. The electron transport material has a parent structure of diversified condensed heterocycles, has high bond energy among atoms, good thermal stability, favorability for solid accumulation among molecules and strong electron transition capability, can effectively reduce the driving voltage of an organic electroluminescent device when being used as an electron transport layer material, improves the current efficiency of the organic electroluminescent device and prolongs the service life of the organic electroluminescent device.
Description
Technical Field
The invention relates to the technical field of luminous display, in particular to an electron transport material, an organic electroluminescent device and a display device.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, etc., compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, the response speed can reach 1000 times of the liquid crystal display, and the manufacturing cost is lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advancement of OLED technology in the two fields of illumination and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is usually the result of the optimized collocation of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, film can be formed on any substrate by a vapor deposition or spin coating method, and flexible display and large-area display can be realized; the optical properties, electrical properties, stability, etc. of the materials can be tuned by changing the structure of the molecules, and the choice of materials has a large space, and in the most common OLED device structures, the following types of organic materials are typically included: a hole injection material, a hole transport material, an electron transport material, a light emitting material (dye or doped guest material) of each color, a corresponding host material, and the like. Currently, an electron transport material is an important functional material, which has a direct effect on the mobility of electrons and ultimately affects the luminous efficiency of an OLED. However, the electron transfer rate achieved by the electron transport materials currently applied to the OLED is low, and the energy level matching with the adjacent layers is poor, which severely restricts the light emitting efficiency of the OLED and the display function of the OLED display device.
Disclosure of Invention
In order to improve the luminous efficiency and prolong the life of an organic light-emitting electroluminescent device, the invention provides an electron transport material, an organic electroluminescent device and a display device.
The electron transport material has a structure shown as a formula I:
wherein,,
Ar 1 -Ar 4 selected from C 6 -C 30 Or C 5 -C 30 The hydrogen atoms of the aryl and heteroaryl groups each independently may be substituted with Ra;
l is selected from chemical bond, C 6 -C 30 Arylene group or C of (C) 3 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
R 1 -R 4 selected from hydrogen, C 1 -C 6 Alkyl, C 6 -C 30 Arylene group or C of (C) 3 -C 30 The hydrogen atoms on the arylene and heteroarylene groups may each independently be substituted with Ra, and adjacent R substituents may be joined to form a ring;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;
ra are each independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably Ar 1 -Ar 4 Selected from one of the following groups, unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, 9-dimethylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothienyl, pyridyl, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, or benzimidazole; l is selected from unsubstituted or taken by RaOne of the subunits of the following compounds is substituted: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, or carbazole; r is R 1 -R 4 Each independently selected from hydrogen, methyl, ethyl, isopropyl, t-butyl, one of the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, or carbazolyl.
The invention also discloses a specific structure of the electron transport material shown in the formulas A1-A30:
the electron transport material has a parent structure of diversified condensed heterocycles, has high bond energy among atoms, good thermal stability, favors solid accumulation among molecules, and strong electron transition capability, can effectively reduce the driving voltage of an organic electroluminescent device when used as an electron transport layer material, improves the current efficiency of the organic electroluminescent device, and prolongs the service life of the organic electroluminescent device; the electron transport material is applied in an electron transport layer, has proper energy level with adjacent layers, is favorable for electron injection and migration, can effectively reduce the landing voltage, has higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device; the electron transport material has a larger conjugate plane, is favorable for molecular accumulation, shows good thermodynamic stability, and shows long service life in an organic electroluminescent device.
The present invention also provides an organic electroluminescent device comprising at least an anode electrode, a hole transporting layer, a light emitting layer, an electron transporting layer and a cathode electrode, wherein the electron transporting layer is at least one selected from the above compounds, and in the present invention, there is no particular limitation on the kind and structure of the organic electroluminescent device as long as the electron transporting material provided by the present invention can be used. The organic electroluminescent device of the present invention may be a light emitting device having a top emission structure, and examples thereof include 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 invention may be a light emitting device having a bottom light emitting structure, and may include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure in this order on a substrate. The organic electroluminescent device of the present invention may be a light emitting device having a double-sided light emitting structure, and may include a transparent or semitransparent 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 structure in this order on a substrate.
Fig. 1 is a schematic structural diagram of a typical organic electroluminescent device according to the present invention, which sequentially includes, from bottom to top: a substrate 1, a reflective anode electrode 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 electrode 8.
For convenience, the organic electroluminescent device of the present invention will be described below with reference to fig. 1, but this is not meant to limit the scope of the present invention in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present invention are within the scope of the present invention.
In the present invention, the substrate 1 is not particularly limited, and a conventional substrate used in the organic electroluminescent device in the related art, such as glass, polymer material, glass with TFT devices, polymer material, and the like, may be used.
In the present invention, the reflective anode electrode 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) 2 ) The transparent conductive material such as zinc oxide (ZnO), the metal material such as silver and its alloy, aluminum and its alloy, or the organic conductive material such as PEDOT (poly 3, 4-ethylenedioxythiophene) is used, and the multilayer structure of the above materials is not particularly limited, and in the present invention, the hole injection layer 3 may be formed using a hole injection layer material known in the art, for example, a Hole Transport Material (HTM) is selected as a host material, and a p-type dopant is added, and the type of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used, for example, the following p-type dopant may be used:
in the present invention, the hole transport layer 4 is not particularly limited, and at least one of a Hole Transport Material (HTM) well known in the art may be selected, for example, a material for a hole injection layer host and a material for a hole transport layer may be selected from at least one of the following HT-1 to HT-32 compounds:
in the present invention, the light emitting material in the light emitting layer 5 is not particularly limited, and any light emitting material known to those skilled in the art may be used, for example, the light emitting material may contain a host material and a light emitting dye. The host material may be selected from at least one of the following GPH-1 to GPH-80 compounds:
preferably, the light emitting layer 5 contains a phosphorescent dopant, and the dopant may be at least one selected from the following RPD-1 to RPD-28 compounds, and the amount of the dopant is not particularly limited and may be an amount known to those skilled in the art.
In the present invention, the electron transport layer 6 contains at least one of the electron transport materials of the present invention, and the electron transport layer 6 may also contain at least one of the electron transport materials of the present invention in combination with at least one of the following known electron transport materials ET-1 to ET-57:
the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and may include, for example, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of materials such as BaO, na, li, ca.
The cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, metals such as magnesium silver mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.
The method of producing the organic electroluminescent device of the present invention is not particularly limited, and any method known in the art may be employed, for example:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top light emission, respectively performing steps of medicine washing, water washing, hairbrushes, high-pressure water washing, air knives and the like in a cleaning machine, and then performing heating treatment;
(2) Vacuum evaporating a hole injection layer 3 on the reflective anode electrode 2, wherein the main material of the hole injection layer is HTM, and the hole injection layer contains P-type dopant (P-dopant) with the thickness of 10-50nm;
(3) Vacuum evaporating a Hole Transport Material (HTM) on the hole injection layer 3 as a hole transport layer 4, wherein the thickness is 80-150nm;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer comprises a host material (GPH) and a guest material (RPD) and has the thickness of 20-50nm;
(5) Vacuum evaporating an Electron Transport Material (ETM) as an electron transport layer 6 on the light emitting layer 5;
(6) Vacuum evaporating an electron injection material on the electron transport layer 6 as an electron injection layer 7;
(7) A cathode material is vacuum-evaporated on the electron injection layer 7 as a cathode electrode 8.
A third aspect of the present invention provides a display device comprising the above organic electroluminescent device, the display device of the present invention including, but not limited to, a display, a television, a tablet computer, a mobile communication terminal, etc.
Detailed Description
The invention is described below in connection with examples which are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
1. Synthesis of electron transport materials
Synthesis of example 1, A1
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of 2-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh) 3 ) 4 Reacting at 60deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The addition amount of (2) chloro-3-phenylquinoxaline is 1mol%;
into a reaction flask were charged 100mmol of M1, 150mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl 2 Reacting at 120deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M2, wherein Pd (dppf) Cl 2 The amount of (C) added is 1mol% of M1;
into a reaction flask were charged 100mmol of 2- (3-chloro-5-bromophenyl) -4, 6-diphenyltriazine, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M3, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 2- (3-chloro-5-bromophenyl) -4, 6-diphenyltriazine;
into a reaction flask were charged 100mmol of M2, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A1, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
The results of the hydrogen spectrum characterization of A1 are as follows:
1 HNMR(400MHz,Chloroform)δ8.86(s,1H),8.46–8.34(m,3H),8.23(s,1H),7.96(d,J＝10.0Hz,2H),7.88(d,J＝8.4Hz,6H),7.80(s,1H),7.75-7.59(m,8H),7.52–7.40(m,8H),7.39(s,1H).
the reaction scheme is as follows:
examples 2, synthesis of A9
Into a reaction flask were charged 100mmol of 2, 3-dichloro-quinoxaline, 100mmol of 4-dibenzofuran-boric acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh 3 ) 4 Reacting at 60deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The addition amount of (2) is 1mol% of 2, 4-dichloroquinazoline;
into a reaction flask were charged 100mmol of M1, 100mmol of 4-chlorophenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M2, wherein Pd (PPh) 3 ) 4 The amount of (C) added is 1mol% of M1;
into a reaction flask were charged 100mmol of M2, 150mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl 2 Reacting at 120deg.C for 12 hr, cooling to room temperature, adding water, filtering, and washingThe solid obtained was purified by recrystallization from toluene to give a white powder M3 in which Pd (dppf) Cl 2 The amount of (2) added is 1mol% of M2;
into a reaction flask were charged 100mmol of 2- (3-chloro-5-bromophenyl) -4, 6-diphenyltriazine, 100mmol of 2-naphthaleneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M4, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 2- (3-chloro-5-bromophenyl) -4, 6-diphenyltriazine;
into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A9, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
The results of the hydrogen spectrum characterization of A9 are as follows:
1 HNMR(400MHz,Chloroform)δ8.62(s,1H),8.51(s,1H),8.42(d,J＝9.6Hz,1H),8.39(d,J＝8.8Hz,4H),8.13(s,1H),8.08(d,J＝12.0Hz,4H),8.03(s,1H),7.99–7.82(m,5H),7.79(d,J＝6.4Hz,2H),7.63(s,1H),7.58(d,J＝8.0Hz,2H),7.55–7.45(m,5H),7.36(d,J＝7.6Hz,2H),7.24(s,1H).
the reaction scheme is as follows:
example 3 Synthesis of A11
Into a reaction flask were charged 100mmol of 2, 3-dichloro-quinoxaline, 100mmol of (3- (pyridin-3-yl) phenyl) boronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, and collecting waterWashing, and recrystallizing the obtained solid with toluene to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The addition amount of (2), 3-dichloro quinoxaline is 1mol%;
into a reaction flask were charged 100mmol of M1, 100mmol of 4-chlorophenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M2, wherein Pd (PPh) 3 ) 4 The amount of (C) added is 1mol% of M1;
into a reaction flask were charged 100mmol of M2, 150mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl 2 Reacting at 120deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M3, wherein Pd (dppf) Cl 2 The amount of (2) added is 1mol% of M2;
into a reaction flask were charged 100mmol of M3, 100mmol of 3-bromo-5-chloro-1, 1' -biphenyl, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M4, wherein Pd (PPh) 3 ) 4 The amount of (2) added is 1mol% of M3;
into a reaction flask were charged 100mmol of M4, 150mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl 2 Reacting at 120deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing with toluene to obtain white powder M5, wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M4;
into a reaction flask were charged 100mmol of 2, 4-dichloro-6-phenyltriazine, 100mmol of 2-boric acid-9, 9-dimethylfluorene, 41.4g of potassium carbonate (300 mmol), 800ml of tetrahydrofuran(THF), 200ml of water and Pd (PPh) 3 ) 4 Reacting at 60deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M6, wherein Pd (PPh) 3 ) 4 The addition amount of (2), 4-dichloro-6-phenyltriazine was 1mol%;
into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A11, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
The results of the A11 hydrogen spectrum are shown below:
1 HNMR(400MHz,Chloroform)δ8.45(d,J＝8.4Hz,2H),8.36(s,1H),8.25(d,J＝6.4Hz,2H),8.09(s,1H),7.97(d,J＝10.0Hz,2H),7.90(s,1H),7.78(t,J＝12.4Hz,4H),7.63(d,J＝10.8Hz,4H),7.60(d,J＝9.6Hz,2H),7.49(d,J＝8.0Hz,6H),7.41(s,1H),7.38–7.16(m,8H),1.69(s,6H).
the reaction scheme is as follows:
example 4 Synthesis of A19
Into a reaction flask were charged 100mmol of 2, 3-dichloro-quinoxaline, 100mmol of isopropylboric acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF), 200ml of water and Pd (PPh) 3 ) 4 Reacting at 60deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The addition amount of (2) is 1mol% of 2, 4-dichloroquinazoline;
into a reaction flask were charged 100mmol of M1, 100mmol of 4-chlorophenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (P)Ph 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M2, wherein Pd (PPh) 3 ) 4 The amount of (C) added is 1mol% of M1;
into a reaction flask were charged 100mmol of M2, 150mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl 2 Reacting at 120deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M3, wherein Pd (dppf) Cl 2 The amount of (2) added is 1mol% of M2;
into a reaction flask were charged 100mmol of 2- (3-chloro-5-bromophenyl) -4, 6-diphenyltriazine, 100mmol of 2-naphthaleneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M4, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 2- (3-chloro-5-bromophenyl) -4, 6-diphenyltriazine;
into a reaction flask were charged 100mmol of M4, 150mmol of pinacol diboronate, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% of Pd (dppf) Cl 2 Reacting at 120deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing with toluene to obtain white powder M5, wherein Pd (dppf) Cl 24 The amount of (2) added is 1mol% of M2;
into a reaction flask were charged 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A19, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
The results of the A19 hydrogen spectrum are shown below:
1 HNMR(400MHz,Chloroform)δ8.61(d,J＝8.0Hz,3H),8.55(s,1H),8.36-8.13(m,3H),8.01(s,1H),7.92(s,1H),7.80(d,J＝7.6Hz,4H),7.65-7.54(m,8H),7.49(d,J＝8.0Hz,4H),3.44(s,1H),1.33(s,6H).
the reaction scheme is as follows:
example 5 Synthesis of A27
Into a reaction flask were charged 100mmol of 2- (3-chloro-5-bromophenyl) -4-phenyl-6- (4-biphenylyl) triazine, 150mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol), 800ml of DMF and 1mol% Pd (dppf) Cl 2 Reacting at 120deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of 2- (3-chloro-5-bromophenyl) -4-phenyl-6- (4-biphenylyl) triazine;
into a reaction flask were charged 100mmol of M1, 100mmol of 2, 3-dichloro-quinoxaline, 41.4g of potassium carbonate (300 mmol), 800ml of THF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder M2, wherein Pd (PPh) 3 ) 4 The amount of (C) added is 1mol% of M1;
into a reaction flask were charged 100mmol of M2, 100mmol of (4- (1-phenyl-1H-benzo [ d)]Imidazole-2-yl-phenyl) phenylboronic acid, 41.4g potassium carbonate (300 mmol), 800ml THF, 200ml water and Pd (PPh) 3 ) 4 Reacting at 80deg.C for 12 hr, cooling to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene to obtain white powder A27, wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
The results of the A27 hydrogen spectrum are shown below:
1 HNMR(400MHz,Chloroform)δ8.56(s,1H),8.49(s,1H),8.36(d,J＝8.4Hz,3H),8.30(s,1H),8.28–7.96(m,6H),7.88–7.77(m,4H),7.75(s,2H),7.63(d,J＝12.0Hz,3H),7.56–7.40(m,11H),7.38(s,2H),7.27(d,J＝11.6Hz,4H).
the reaction scheme is as follows:
2. preparation of organic electroluminescent device
Ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in an acetone-ethanol mixed solvent, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
placing the above glass substrate with anode in vacuum cavity, and vacuumizing to less than 10 -5 And vacuum evaporation of a hole injection layer on the anode layer film, wherein the hole injection layer is made of HT-4 and 3% of p-type dopant (p-dopant) by mass ratio, the evaporation rate is 0.1nm/s, the thickness of the evaporation film is 10nm, and the hole injection layer is made of the following materials:
vacuum evaporating a hole transport material HT-5 on the hole injection layer to serve as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 80nm;
vacuum evaporation plating a light-emitting layer on the hole transport layer, wherein the light-emitting layer comprises a main material GHP-16 and a dye material RPD-1, and evaporation plating is carried out by utilizing a multi-source co-evaporation method, wherein the evaporation plating rate of the main material GHP-16 is regulated to be 0.1nm/s, the evaporation plating rate of the dye RPD-1 is 3% of the evaporation plating rate of the main material, and the total evaporation plating film thickness is 30nm;
vacuum evaporating an Electron Transport Layer (ETL) on the luminescent layer, wherein the electron transport layer is the electron transport material prepared in the embodiments 1-5, respectively, liF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) as an electron injection layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10nm; finally, an aluminum layer with the thickness of 150nm is vacuum-evaporated on the electron injection layer to serve as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate is 1nm/s, and the thickness of the evaporation film is 50nm.
Comparative example 1
The electron transport material ET-16 of the organic electroluminescent device is replaced by a substance with the following structure, and the rest is unchanged.
The organic electroluminescent devices of examples 1 to 4 and comparative example 1 were subjected to the following performance measurements:
under the same brightness, using a digital source meter and a brightness meter to measure the driving voltage and current efficiency of the organic electroluminescent device and the service life of the device, specifically, increasing the voltage at a rate of 0.1V per second to measure that the brightness of the organic electroluminescent device reaches 5000cd/m 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; the lifetime test of LT95 is as follows: at 5000cd/m using a luminance meter 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 4750cd/m 2 Time in hours. The results are shown in Table 1.
TABLE 1 organic electroluminescent device Performance
| Required brightness (cd/m) 2 ) | Drive voltage/V | Current efficiency (cd/A) | Lifetime (LT 95)/h | |
| Example 1 | 5000.00 | 4.1 | 42.5 | 260 |
| Example 2 | 5000.00 | 3.8 | 42.8 | 275 |
| Example 3 | 5000.00 | 4.0 | 41.6 | 270 |
| Example 4 | 5000.00 | 3.9 | 43.2 | 280 |
| Example 5 | 5000.00 | 4.0 | 42.5 | 270 |
| Comparative example 1 | 5000.00 | 4.4 | 37.4 | 215 |
As can be seen from Table 1, the compounds A1, A9, A11, A19 and A27 prepared by the method are used for the electron transport material of the organic electroluminescent device, can effectively reduce the driving voltage, improve the current efficiency, prolong the service life of the device, and are electron transport materials with good performance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (4)
1. An electron transport material characterized by having a structure represented by the formulas A1, A9, a11, a19, and a 27:
2. an organic electroluminescent device comprising an anode electrode, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode electrode, wherein the electron transporting layer comprises at least one of the electron transporting materials of claim 1.
3. The organic electroluminescent device of claim 2, wherein the electron transport layer further comprises at least one transport material of the formulae ET-1 to ET-57, the formulae ET-1 to ET-57 having the structure,
4. a display device comprising the organic electroluminescent device as claimed in claim 2 or 3.
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