CN104629738A - Bipolar blue-ray phosphorescent host material, preparation method thereof and organic electroluminescent device - Google Patents
Bipolar blue-ray phosphorescent host material, preparation method thereof and organic electroluminescent device Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 241001025261 Neoraja caerulea Species 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
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- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 229940126062 Compound A Drugs 0.000 claims description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
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- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- SROUTDZAHLYYOQ-UHFFFAOYSA-N [Ir]C=O.C1=CC=NC=C1 Chemical compound [Ir]C=O.C1=CC=NC=C1 SROUTDZAHLYYOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- 0 CC(C=CC(c1cc(-c2cc(-c(ccc3nc(-c4ccccc4)c4)cc3c4-c3ccccc3)ccc2*2c3ccccc3)c2cc1)=C1)C1=C(C=C(c1ccccc1)N)c1ccccc1 Chemical compound CC(C=CC(c1cc(-c2cc(-c(ccc3nc(-c4ccccc4)c4)cc3c4-c3ccccc3)ccc2*2c3ccccc3)c2cc1)=C1)C1=C(C=C(c1ccccc1)N)c1ccccc1 0.000 description 5
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- VUQCHOGXZNSPHL-UHFFFAOYSA-N 6-bromo-2,4-diphenylquinoline Chemical compound C12=CC(Br)=CC=C2N=C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 VUQCHOGXZNSPHL-UHFFFAOYSA-N 0.000 description 4
- OYPIMRRBVHIMLW-UHFFFAOYSA-N 9-phenyl-2,3,4,5,6,7,9,10-octahydroacridine-1,8-dione Chemical compound O=C1CCCC(NC2=C3C(CCC2)=O)=C1C3C1=CC=CC=C1 OYPIMRRBVHIMLW-UHFFFAOYSA-N 0.000 description 4
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical group [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
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- IUAHTFPYYKMWIP-UHFFFAOYSA-N c(cc1)ccc1-c1c(cc(cc2)-c(cc3)cc(c4cc(-c(cc5)cc(c(-c6ccccc6)c6)c5nc6-c5ccccc5)ccc44)c3[n]4-c3ccccc3)c2nc(-c2ccccc2)c1 Chemical compound c(cc1)ccc1-c1c(cc(cc2)-c(cc3)cc(c4cc(-c(cc5)cc(c(-c6ccccc6)c6)c5nc6-c5ccccc5)ccc44)c3[n]4-c3ccccc3)c2nc(-c2ccccc2)c1 IUAHTFPYYKMWIP-UHFFFAOYSA-N 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the field of organic electroluminescent materials, and discloses a bipolar blue-ray phosphorescent host material, as well as a preparation method and an organic electroluminescent device thereof. The material has a structural formula as shown in the specification. In the bipolar blue-ray phosphorescent host material, carbazole is an electron-enriched nitrogenous heterocyclic aromatic hydrocarbon, and has an excellent hole transmission performance; and quinoline is a relatively good electron transmission unit. Therefore, the material simultaneously has hole transmission property and electron transmission property to balance hole and electron transmission in a luminescent layer, and has relatively high triplet state level to effectively prevent energy from being returned to the host material in the luminescence process, so that the luminescence efficiency is greatly improved.
Description
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a bipolar blue-light phosphorescent host material and a preparation method thereof. The invention also relates to an organic electroluminescent device adopting the bipolar blue-light phosphorescent host material as a host material of a light-emitting layer.
Background
The organic electroluminescent device has the advantages of low driving voltage, high response speed, wide visual angle range, abundant colors due to the fact that the luminous performance can be changed through fine adjustment of a chemical structure, high resolution, light weight, large-area panel display and the like, is known as a panel display technology in the 21 st century, and becomes a hotspot of research in the fields of materials, information, physics and other subjects and panel display. Future efficient commercial organic light emitting diodes will likely contain organometallic phosphors because they can trap both singlet and triplet excitons, achieving 100% internal quantum efficiency. However, due to the relatively long excited exciton lifetime of the transition metal complexes, unwanted triplet-triplet (T) results1-T1) Quenching in the actual operation of the device. To overcome this problem, researchers often dope triplet emitters into organic host materials.
In recent years, green and red phosphorescent OLED devices have exhibited satisfactory electroluminescent efficiency. While highly efficient blue phosphorescent devices are rare, the main reason is the lack of a combination of good carrier transport properties and high triplet energy level (E)T) The host material of (1).
Disclosure of Invention
The invention aims to provide a bipolar blue light phosphorescent host material with higher carrier transport performance and triplet state energy level.
In order to achieve the purpose, the bipolar blue light phosphorescent host material provided by the invention has the following structure:
i.e. 3, 6-bis (2, 4-diphenylquinolin-6-yl) -9-phenyl-9H-carbazole.
Another objective of the present invention is to provide a method for preparing a bipolar blue-light phosphorescent host material, which has a simple synthetic route and is cheap and easily available, and the method comprises the following steps:
compounds A and B are provided, respectively, represented by the following structural formulae,
adding a compound A and a compound B into an organic solvent containing a catalyst and an alkali solution in an oxygen-free environment for dissolving, wherein the molar ratio of the compound A to the compound B is 1: 2-2.4, carrying out Suzuki coupling reaction on a mixed solution obtained after dissolving at 70-130 ℃ for 12-48 hours, stopping the reaction, cooling to room temperature, and separating and purifying the reaction solution to obtain the bipolar blue-light phosphorescent host material with the following structural formula:
wherein the catalyst is bis-triphenylphosphine palladium dichloride or tetrakis triphenylphosphine palladium; or,
the catalyst is a mixture of organic palladium and an organic phosphine ligand, and the molar ratio of the organic palladium to the organic phosphine ligand is 1: 4-8; preferably, the organic palladium is palladium acetate or tris-argon benzyl acetone dipalladium, and the organic phosphine ligand is tris (o-methylphenyl) phosphine or 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl; more preferably, the mixture is a mixture of palladium acetate and tris (o-methylphenyl) phosphine, or the mixture is a mixture of tris-argon benzylacetone dipalladium and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
The molar ratio of the catalyst to the compound A is 1: 20-1: 100.
In the preparation method, the alkali solution is at least one selected from a sodium carbonate solution, a potassium carbonate solution and a sodium bicarbonate solution; in the alkaline solution, the molar ratio of the alkaline solute to the compound A is 20: 1.
In a preferred embodiment, the organic solvent is selected from at least one of toluene, N-dimethylformamide, tetrahydrofuran.
In a preferred embodiment, the reaction temperature of the Suzuki coupling reaction is 90-120 ℃, and the reaction time is 24-36 hours.
In a preferred embodiment, the separation and purification reaction liquid includes:
after Suzuki coupling reaction is stopped, extracting reaction liquid by using dichloromethane for multiple times, merging organic phases, drying the organic phases by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the bipolar blue-light phosphorescent main body material.
In the preparation method, the oxygen-free environment is composed of at least one gas of argon and nitrogen.
The preparation method has the advantages of simple principle, simple and convenient operation, low requirement on equipment and wide popularization and application.
The invention also aims to provide application of the bipolar blue phosphorescent host material in a light-emitting layer of an organic electroluminescent device.
The organic electroluminescent device structurally comprises a conductive anode substrate, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially stacked on the conductive anode substrate; wherein:
the conductive anode substrate comprises a glass substrate and a conductive anode layer deposited on the surface of the glass substrate, wherein the conductive anode layer is made of Indium Tin Oxide (ITO);
the hole injection layer is made of PEDOT (PSS);
the material of the hole transport layer is N, N '-di [ (1-naphthyl) -N, N' -diphenyl ] -1,1 '-biphenyl-4, 4' -diamine (NPD);
the material of the light emitting layer is the bipolar blue light phosphorescence host material, namely, a doped mixed material formed by doping 8 mass percent of bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyl iridium (FIrpic) guest material with 3, 6-bis (2, 4-diphenylquinoline-6-yl) -9-phenyl-9H-carbazole as the host material;
the material of the electron transport layer is 8-hydroxyquinoline aluminum (Alq 3);
the electron injection layer is made of LiF;
the cathode layer is made of Al.
In the bipolar blue light phosphorescence host material provided by the invention, carbazole is an electron-rich nitrogen-containing heterocyclic aromatic compound and has excellent hole transport performance; quinoline is a preferred electron transport unit. Therefore, the material has both hole transport property and electron transport property, so that the transport of holes and electrons in the light-emitting layer is balanced; the material also has a high triplet state energy level, so that energy is effectively prevented from being transmitted back to the main material in the light emitting process, and the light emitting efficiency is greatly improved.
The preparation method of the bipolar blue-light phosphorescent host material adopts a simpler synthesis route, thereby reducing the process flow, and the raw materials are cheap and easy to obtain, so that the manufacturing cost is reduced.
Drawings
FIG. 1 is a thermogravimetric analysis chart of the ambipolar blue phosphorescent host material prepared in example 1;
fig. 2 is a schematic view of the structure of an organic electroluminescent device prepared in example 5.
Detailed Description
For better understanding of the contents of the present patent, the technical scheme of the present invention is further illustrated below by specific examples and illustrations, including material preparation and device preparation, but the present invention is not limited by these examples, wherein compound a and compound B are both available from carbofuran technology.
Example 1: the bipolar blue-light phosphorescent host material of the embodiment, namely 3, 6-bis (2, 4-diphenylquinolin-6-yl) -9-phenyl-9H-carbazole, has the following structural formula:
the preparation process of the compound comprises the following steps:
under the protection of argon, 9-phenyl-3, 6-dipinacolone borate-9H-carbazole (99mg,0.2mmol) and 6-bromo-2, 4-diphenylquinoline (144mg,0.4mmol) are added into a flask containing 10mL of toluene solvent, after full dissolution, a potassium carbonate (2mL,2mol/L) solution is added into the flask, vacuum pumping is performed to remove oxygen, argon is filled, and then bis-triphenylphosphine palladium dichloride (5.6 mg,0.008 mmol) is added; will be provided withThe flask was heated to 120 ℃ for a Suzuki coupling reaction for 24 h. Stopping the reaction and cooling to room temperature, extracting the reaction liquid by using dichloromethane after the Suzuki coupling reaction is stopped, merging an organic phase for multiple times, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the bipolar blue-light phosphorescent main body material. The yield was 84%. Mass spectrum: m/z802.0 (M)++ 1); elemental analysis (%) C60H39N3Theoretical value: c89.86, H4.90, N5.24; measured value: c89.85, H4.82, N5.20.
FIG. 1 is a thermogravimetric analysis chart of the ambipolar blue phosphorescent host material prepared in example 1; thermogravimetric analysis was performed by a Perkin-Elmer Series7 thermoanalysis system, all measurements being performed in a room temperature atmosphere. As shown in FIG. 1, the thermal weight loss temperature (T) of the bipolar blue-light phosphorescent host material is 5%d) Is 388 ℃.
Example 2: the bipolar blue-light phosphorescent host material of the embodiment has a structure of 3, 6-bis (2, 4-diphenylquinolin-6-yl) -9-phenyl-9H-carbazole, and the structural formula is as follows:
the preparation process of the compound comprises the following steps:
under the protection of a mixed gas of nitrogen and argon, 9-phenyl-3, 6-dipinacolone borate-9H-carbazole (149mg,0.3mmol), 6-bromo-2, 4-diphenylquinoline (238mg,0.66mmol) and 15mL of tetrahydrofuran are added into a 50 mL-specification two-neck bottle, after full dissolution, mixed gas of nitrogen and argon is introduced to exhaust air for about 20min, then palladium (4 mg,0.003 mmol) of tetratriphenylphosphine is added, and after full dissolution, a sodium bicarbonate (3mL,2mol/L) solution is added. After the mixture of nitrogen and argon was fully purged for about 10min, the two bottles were charged to 70 ℃ to conduct Suzuki coupling reaction for 48 hours. Stopping the reaction and cooling to room temperature, extracting the reaction liquid by using dichloromethane after the Suzuki coupling reaction is stopped, merging an organic phase for multiple times, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the bipolar blue-light phosphorescent main body material. The yield was 81%.
Example 3: the bipolar blue-light phosphorescent host material of the embodiment has a structure of 3, 6-bis (2, 4-diphenylquinolin-6-yl) -9-phenyl-9H-carbazole, and the structural formula is as follows:
the preparation process of the compound comprises the following steps:
adding 9-phenyl-3, 6-dipinacolone borate-9H-carbazole (149mg,0.3mmol), 6-bromo-2, 4-diphenylquinoline (259mg,0.72mmol), palladium acetate (3.5mg,0.015mmol) and tris (o-methylphenyl) phosphine (21mg, 0.06mmol) into a flask containing 12mL of N, N-dimethylformamide under the protection of nitrogen, adding a potassium carbonate (3mL,2mol/L) solution after sufficient dissolution, and then introducing nitrogen into the flask to evacuate air for about 30 min; the flask was heated to 130 ℃ for a Suzuki coupling reaction for 12 h. Stopping the reaction and cooling to room temperature, extracting the reaction liquid by using dichloromethane after the Suzuki coupling reaction is stopped, merging an organic phase for multiple times, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the bipolar blue-light phosphorescent main body material. The yield was 78%.
Example 4: the bipolar blue-light phosphorescent host material of the embodiment has a structure of 3, 6-bis (2, 4-diphenylquinolin-6-yl) -9-phenyl-9H-carbazole, and the structural formula is as follows:
the preparation process of the compound comprises the following steps:
9-phenyl-3, 6-dipinacolonic borate-9H-carbazole (149mg,0.3mmol), 6-bromo-2, 4-diphenylquinoline (248mg,0.69mmol), tris-argon-benzylacetone dipalladium (9mg,0.009mmol), and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (29mg, 0.072mmol) were added to a flask containing 12mL of N, N-dimethylformamide under nitrogen, and after sufficient dissolution, a solution of sodium carbonate (3mL,2mol/L) was added. Then introducing nitrogen into the flask to exhaust air for about 30 min; the flask was heated to 90 ℃ for a Suzuki coupling reaction for 36 h. Stopping the reaction and cooling to room temperature, extracting the reaction liquid by using dichloromethane after the Suzuki coupling reaction is stopped, merging an organic phase for multiple times, drying the organic phase by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the bipolar blue-light phosphorescent main body material. The yield was 85%.
Example 5:
the organic electroluminescent device 300 provided in this embodiment, as shown in fig. 2, has a structure including a substrate 301, an anode 302, a hole injection layer 303, a hole transport layer 304, a light emitting layer 305, an electron transport layer 306, an electron injection buffer layer 307, and a cathode 308.
In this embodiment, the substrate 301 is made of glass, an anode 302, a hole injection layer 303, a hole transport layer 304, a light emitting layer 305, an electron transport layer 306, an electron injection buffer layer 307, and a cathode 308 are sequentially vacuum-coated on the substrate 301, the anode 302 is made of indium tin oxide with a sheet resistance of 10 to 20 Ω/□, the thickness is 150nm, the hole injection layer 303 is made of poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid, the thickness is 30nm, the hole transport layer 304 is made of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, the thickness is 20nm, the host material of the light emitting layer 305 is 3, 6-bis (2, 4-diphenylquinolin-6-yl) -9-phenyl-9H-carbazole prepared by the present invention, and a guest material of bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyl iridium (III) with the mass percent of 8% is doped by taking a host material as a reference, the thickness of a luminescent layer 305 is 20nm, an electron transport layer 306 adopts Alq3 and tris (8-hydroxyquinoline) aluminum with the thickness of 30nm, an electron injection buffer layer 307 adopts lithium fluoride with the thickness of 1.5nm, and a cathode 308 adopts metallic aluminum with the thickness of 150 nm.
The hole injection layer 303, the hole transport layer 304, the light emitting layer 305, the electron transport layer 306, the electron injection buffer layer 307 and the cathode 308 are deposited by thermal evaporation process with a vacuum degree of 10-3～10-5pa, the thickness of the thin film is monitored by a film thickness monitor, and the evaporation rate of all materials except the guest material of the light-emitting layer isPer second, evaporation rate of lithium fluoride ofIn seconds, the evaporation rate of metallic aluminum isIn seconds.
The electroluminescent device has high luminous efficiency and can be widely applied to the blue or white light emitting field. The current-luminance-voltage characteristics of the device were all measurements made by a Keithley source measurement system (Keithley 2400 Sourcemeter) with calibrated silicon photodiodes in a room temperature atmosphere. The results show that: the starting voltage of the device is 4.3V, and the lumen efficiency is 8.5lm/W under the brightness of 1000cd/m 2.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A bipolar blue light phosphorescence host material is characterized in that the structure is as follows:
2. the preparation method of the bipolar blue-light phosphorescent host material as claimed in claim 1, characterized by comprising the following steps:
compounds A and B are provided, respectively, represented by the following structural formulae,
adding a compound A and a compound B with a molar ratio of 1: 2-2.4 into an organic solvent containing a catalyst and an alkali solution in an oxygen-free environment for dissolving, carrying out Suzuki coupling reaction on the obtained mixed solution at 70-130 ℃ for 12-48 hours, stopping the reaction, cooling to room temperature, and separating and purifying the reaction solution to obtain the bipolar blue-light phosphorescent host material with the following structural formula:
3. the preparation method of the bipolar blue-light phosphorescent host material according to claim 2, wherein the catalyst is bis-triphenylphosphine palladium dichloride or tetrakis-triphenylphosphine palladium; the molar ratio of the catalyst to the compound A is 1: 20-1: 100.
4. The preparation method of the bipolar blue-light phosphorescent host material according to claim 2, wherein the catalyst is a mixture of organic palladium and an organic phosphine ligand, and the molar ratio of the organic palladium to the organic phosphine ligand is 1: 4-8; the molar ratio of the catalyst to the compound A is 1: 20-1: 100.
5. The preparation method of the bipolar blue-light phosphorescent host material according to claim 4, wherein the organic palladium is palladium acetate or tris-argon benzyl acetone dipalladium, and the organic phosphine ligand is tris (o-methylphenyl) phosphine or 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
6. The method for preparing a bipolar blue-light phosphorescent host material as claimed in claim 5, wherein the mixture is a mixture of palladium acetate and tris (o-methylphenyl) phosphine, or the mixture is a mixture of tris-argon-benzylacetone dipalladium and 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl.
7. The method of claim 2, wherein the alkali solution is at least one selected from sodium carbonate solution, potassium carbonate solution, and sodium bicarbonate solution; in the alkaline solution, the molar ratio of the alkaline solute to the compound A is 20: 1.
8. The method of claim 2, wherein the organic solvent is at least one selected from the group consisting of toluene, N-dimethylformamide, and tetrahydrofuran.
9. The method of any one of claims 2 to 8, wherein the separating and purifying the reaction solution comprises:
after Suzuki coupling reaction is stopped, extracting reaction liquid by using dichloromethane for multiple times, merging organic phases, drying the organic phases by using anhydrous magnesium sulfate, and then carrying out spin drying to obtain a crude product, separating the crude product by using petroleum ether and ethyl acetate mixed eluent with the volume ratio of 10:1 through a silica gel chromatographic column to obtain a crystal substance, and drying the crystal substance at 50 ℃ in vacuum for 24 hours to obtain the bipolar blue-light phosphorescent main body material.
10. An organic electroluminescent device is characterized in that a luminescent layer is made of a doped mixed material formed by doping a host material with 8 mass percent of a guest material; the host material is the bipolar blue-light phosphorescent host material as claimed in claim 1, and the guest material is bis (4, 6-difluorophenylpyridine-N, C2) pyridine formyliridium.
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