CN115974873A - Rare earth complex, preparation method thereof and organic electroluminescent device - Google Patents
Rare earth complex, preparation method thereof and organic electroluminescent device Download PDFInfo
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- CN115974873A CN115974873A CN202310057510.1A CN202310057510A CN115974873A CN 115974873 A CN115974873 A CN 115974873A CN 202310057510 A CN202310057510 A CN 202310057510A CN 115974873 A CN115974873 A CN 115974873A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 67
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims description 44
- 238000012986 modification Methods 0.000 claims description 34
- 230000004048 modification Effects 0.000 claims description 34
- 229910052741 iridium Inorganic materials 0.000 claims description 21
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 20
- 230000005525 hole transport Effects 0.000 claims description 19
- 230000000903 blocking effect Effects 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 12
- YERGTYJYQCLVDM-UHFFFAOYSA-N iridium(3+);2-(4-methylphenyl)pyridine Chemical compound [Ir+3].C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1 YERGTYJYQCLVDM-UHFFFAOYSA-N 0.000 claims description 11
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
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- -1 4-tert-butylphenyl Chemical group 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 claims description 8
- UFWDOFZYKRDHPB-UHFFFAOYSA-N 9-[3-[6-(3-carbazol-9-ylphenyl)pyridin-2-yl]phenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(C=2C=CC=C(N=2)C=2C=CC=C(C=2)N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 UFWDOFZYKRDHPB-UHFFFAOYSA-N 0.000 claims description 7
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- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 claims description 5
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 4
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- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application provides a rare earth complex [ Gd (DPPDA) 2 ](TOA), the rare earth complex has simple preparation steps and is convenient for industrial production; the rare earth complex provided by the invention is used for sensitizing an organic electroluminescent device, and the performance test of the sensitized organic electroluminescent device shows that the rare earth complex [ Gd (DPPDA) ]is prepared by using the rare earth complex 2 ]The performance of The (TOA) sensitized organic electroluminescent device is good.
Description
Technical Field
The invention belongs to the field of organic light-emitting diodes, and particularly relates to a rare earth complex, a preparation method thereof and an organic electroluminescent device.
Background
The rare earth complex is a luminescent material with special performance, and a ligand absorbs energy by virtue of an antenna effect and transfers the energy to a rare earth central ion, and then the rare earth ion radiates transition luminescence. Since the rare earth ion 4f orbital electron layer is shielded by the outer 5s5p orbital electron, the electron energy level is little affected by the external coordination field and the electric field, and most rare earth ions have the luminescent characteristic of high color purity. Meanwhile, 4f-4f radiation transition of rare earth ions is sterically forbidden, so that the excited state of the rare earth complex has longer service life.
In Organic Light Emitting Diodes (OLEDs), their long excited state lifetime is beneficial for achieving intermolecular energy transfer. The screening of the triplet energy-matched rare earth complex can play a role of energy transfer step, is beneficial to accelerating the energy transfer from the main material molecules to the luminescent material molecules, and further improves the utilization rate of excitons. In addition, the wide band gap characteristic of the rare earth complex endows the rare earth complex with stronger carrier capture capacity, rare earth complex molecules are introduced into an OLEDs light emitting layer by utilizing a micro doping technology and are used as carrier capture centers to capture excess carriers preferentially, so that the carrier distribution on the light emitting molecules can be balanced, and the annihilation of excitons by the excess carriers is reduced.
In recent years, with the rapid development of the material synthesis and device preparation fields, rare earth complexes have been widely researched and applied as sensitizers in OLEDs. For example, rare earth europium (Eu) complexes are used to sensitize red OLEDs, rare earth terbium (Tb) complexes are used to sensitize green OLEDs, and rare earth gadolinium (Gd) complexes are used to sensitize white OLEDs. For example, document j.mater.chem.c,2017,5,2066 discloses a rare earth Gd complex, which is used in an organic electroluminescent device, and the obtained device has good performance, but the complex is complicated in preparation method and not beneficial to industrial production.
Disclosure of Invention
In view of the above, the present invention provides a rare earth complex, a preparation method thereof, and an organic electroluminescent device, where the rare earth complex can be used to sensitize OLEDs to make the OLEDs have good performance, and the rare earth complex has simple preparation steps and is convenient for industrialization.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a rare earth complex with a structure of formula (I):
the present invention provides an organic electroluminescent device comprising: a first electrode, a second electrode, and a light-emitting layer disposed between the first electrode and the second electrode, the light-emitting layer comprising the rare earth complex of claim 1 and a light-emitting material.
Preferably, the light emitting layer includes a hole-dominant light emitting layer and an electron-dominant light emitting layer, and the electron-dominant light emitting layer includes the rare earth complex according to claim 1.
Preferably, the content of the rare earth complex in the electron-dominated light-emitting layer is 0.1 to 1.0wt%, and the content of the light-emitting material in the electron-dominated light-emitting layer is 1 to 20wt%.
In some specific implementations, the organic electroluminescent device further includes optionally the following structure:
a hole transport layer disposed between the first electrode and the hole-dominant emission layer;
an electron transport layer disposed between the second electrode and the electron-dominated light-emitting layer.
In some embodiments, the organic electroluminescent device further comprises optionally the following structure:
an electron blocking layer disposed between the hole transport layer and the hole-dominant emission layer;
a hole blocking layer disposed between the electron transporting and electron dominated light emitting layers.
Preferably, the hole-dominated light-emitting layer comprises an organic light-emitting material and a hole-type organic host material, the organic light-emitting material is [ bis (2-phenylquinoline) ] (2,2,6,6-tetramethylheptane-3,5-heptanedionate) iridium (III), tris [2- (p-tolyl) pyridine ] iridium (III), bis (2- (9,9-diethyl-fluoren-2-yl) -1-phenyl-1H-benzo [ d ] imidazole) iridium (III) acetylacetonate, tris (2-phenylpyridine) iridium (III) or tris [2- (4-N-hexylphenyl) quinoline ] iridium (III), and the hole-type organic host material is 4,4',4 ″ -tris (carbazol-9-yl) triphenylamine, 4,4', -N, N ' -dicarbazolyl-biphenyl or tris [4- (9-phenylfluorene) phenyl ] amine.
Preferably, the electron dominant emission layer comprises the rare earth complex of claim 1, an organic light emitting material and an electron type organic host material, the organic light emitting material is [ bis (2-phenylquinoline) ] (2,2,6,6-tetramethylheptane-3,5-heptanedionate) iridium (III), tris [2- (p-tolyl) pyridine ] iridium (III), bis (4,6-difluorophenylpyridine-N, C2) picolinoyl iridium, tris (2-phenylpyridine) iridium (III) or tris [2- (4-N-hexylphenyl) quinoline ] iridium (III); the electronic organic main body material is 2,6-bis [3- (9H-9-carbazolyl) phenyl ] pyridine, 9- (4-tert-butylphenyl) -3,6-bis (triphenylsilyl) -9H-carbazole, tris (8-hydroxyquinoline) aluminum (III) or 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene.
In some specific implementations, the hole transport layer is a bipyrazino [2,3-f:2',3' -H ] quinoxaline-2,3,6,7, 10, 11-hexanenitrile, 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], N ' -diphenyl-N, N ' -bis (1-naphthyl) (1,1 ' -diphenyl) -4,4' -diamine and 4,4', 4' -tris [ phenyl (m-tolyl) amino ] triphenylamine, the electron transport layer/hole barrier layer being one or more of 1,3,5-tris (6- (3- (pyridin-3-yl) phenyl) pyridin-2-yl) benzene, 1,3,5-tris- (3-pyridyl-3-phenyl) benzene or 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1,2,4-triaza.
In some embodiments, the first electrode comprises an anode layer and an anode modification layer, the anode layer is ITO glass with an electrode, and the anode modification layer is dipyrazino [2,3-f:2',3' -h ] quinoxaline-2,3,6,7, 10, 11-hexanenitrile, wherein the second electrode is a cathode layer and a cathode modification layer, the cathode layer is Al metal, and the cathode modification layer is LiF.
The invention provides a rare earth complex with the structure of the formula (I), and compared with the prior art, the complex has simple preparation steps and is convenient for industrial production; the rare earth complex provided by the invention is used for sensitizing OLEDs, and an OLEDs device is provided, and the performance test is carried out on the OLEDs device, and the test result shows that the OLEDs sensitized by the rare earth complex provided by the invention have good performance.
Drawings
FIG. 1 is a schematic diagram of the structure of OLEDs;
FIG. 2 shows a rare earth gadolinium complex [ Gd (DPPDA) ]according to the present invention 2 ](TOA) thermogravimetric curve;
FIG. 3 shows a rare earth gadolinium complex [ Gd (DPPDA) ] 2 ](TOA) low temperature phosphorescence spectrum;
FIG. 4 shows a rare earth gadolinium complex [ Gd (DPPDA) ]according to the present invention 2 ](TOA) ultraviolet-visible absorption spectrum;
FIG. 5 shows a rare earth gadolinium complex [ Gd (DPPDA) ] 2 ](TOA) sensitized Red OLEDs at luminance of 20000cd/m 2 Electroluminescence spectrum of time;
FIG. 6 shows a rare earth gadolinium complex [ Gd (DPPDA) ]according to the present invention 2 ](TOA) sensitized green OLEDs having a luminance of 20000cd/m 2 Electroluminescence spectrum of time;
FIG. 7 shows a rare earth gadolinium complex [ Gd (DPPDA) ]according to the present invention 2 ](TOA) electroluminescence spectrum of sensitized white light OLEDs at a current density of 10 mA;
FIG. 8 shows a rare earth gadolinium complex [ Gd (DPPDA) ]according to the present invention 2 ]Voltage-current density-luminance characteristic curves of (TOA) sensitized white light OLEDs;
FIG. 9 shows a rare earth gadolinium complex [ Gd (DPPDA) ]according to the present invention 2 ]Current density-power efficiency-current efficiency characteristic curves for (TOA) sensitized white light OLEDs.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a rare earth complex [ Gd (DPPDA) with a structure of a formula (I) 2 ](TOA)。
In some possible implementations, the rare earth complex [ Gd (DPPDA) ] 2 ](TOA) is prepared by reacting a ligand with a structure shown in a formula (II) with Trioctylamine (TOA) and gadolinium salt.
The ligand can be prepared by the reaction of bathocuproine, selenium dioxide and nitric acid solution.
Specifically, bathocuproine firstly reacts with selenium dioxide, the mass ratio of bathocuproine to selenium dioxide is 1:1-2, and 1.4-1.5 is preferred; the reaction solvent is preferably a mixed solution of dioxane and deionized water, the volume ratio of dioxane to deionized water is 22-24, preferably 23; the reaction temperature is 100-110 ℃, and preferably 105 ℃; the reaction time is 3 to 24 hours, preferably 3 hours, 12 hours or 24 hours. After the bathocuproine and the selenium dioxide react, the bathocuproine and the selenium dioxide react with a nitric acid solution to obtain a ligand, the solvent is removed before the reaction with the nitric acid solution, preferably the solvent is removed by adopting a decompression mode, the mass concentration of the nitric acid solution is 45-50%, preferably 48%, and the dosage relation of the bathocuproine and the nitric acid solution is 1g: 40-45 mL, the reaction temperature is 100-110 ℃, and the optimal temperature is 105 ℃; the reaction time is 3-24 h, preferably 3h, 12h or 24h, after the reaction is finished, filtering and washing are carried out, preferably deionized water and glacial acetonitrile are adopted for washing, drying is carried out after washing, and preferably vacuum heating drying is adopted for obtaining the ligand.
The ligand may be commercially available, and the source of the ligand is not particularly limited in the present invention.
Reacting ligand with Trioctylamine (TOA) and gadolinium salt to obtain rare earth complex [ Gd (DPPDA) 2 ](TOA), the reaction equation is as follows:
in some possible implementations, the ligand and the solvent are mixed, the solvent is aliphatic alcohol, preferably ethanol, and the amount of the ligand and the reaction solvent is 1g: adding trioctylamine in 20-25 mL, wherein the dosage relationship of the ligand and the trioctylamine is 1g; after the ligand is dissolved, gadolinium salt is added, the mass ratio of the ligand to the gadolinium salt is 3-4:1, the gadolinium salt is preferably gadolinium chloride, in some possible implementation modes, the gadolinium salt is prepared into an alcoholic solution of the gadolinium salt for use, the reaction is carried out at room temperature, the reaction time is 4-24 hours, preferably 4 hours, 12 hours or 24 hours, washing is carried out, preferably, the gadolinium salt is washed by a reaction solvent, drying is carried out after the washing is finished, preferably, vacuum heating drying is carried out, a crude product is obtained after the drying, the crude product is recrystallized, preferably, a mixed solvent of ethanol and dichloromethane is used for recrystallization, and the rare earth complex [ Gd (DPPDA) is obtained 2 ](TOA)。
The rare earth complex provided by the invention has simple preparation steps, is beneficial to industrial production, and can be used for preparing the rare earth complex [ Gd (DPPDA) 2 ](TOA) is characterized, and experimental results show that the rare earth complex has good thermal stability, has a triplet state energy level conforming to organic electroluminescent devices (OLEDs) and a larger energy level band gap, and can be used for sensitizing the OLEDs.
The present invention provides OLEDs comprising: a first electrode, a second electrode and a light-emitting layer, the light-emitting layer including the rare earth complex according to claim 1 and a light-emitting material; in some possible implementations, the light emitting layer includes a hole-dominant light emitting layer and an electron-dominant light emitting layer, the electron-dominant light emitting layer including the rare earth complex of claim 1; in some possible implementations, the organic electroluminescent device further includes optionally the following structure: a hole transport layer disposed between the first electrode and the hole-dominated light-emitting layer, an electron transport layer disposed between the second electrode and the electron-dominated light-emitting layer, an electron blocking layer disposed between the hole transport layer and the hole-dominated light-emitting layer, and a hole blocking layer disposed between the electron transport and electron-dominated light-emitting layers.
Specifically, the hole-dominant light-emitting layer comprises an organic light-emitting material and a hole-type organic host material, wherein the organic light-emitting material is [ bis (2-phenylquinoline)](2,2,6,6-tetramethylheptane-3,5-heptanedionic acid) Iridium (III) (abbreviation (PQ) 2 Ir (dpm)), tris [2- (p-tolyl) pyridine]Iridium (III) (Ir (mppy) for short) 3 ) Bis (2- (9,9-diethyl-fluoren-2-yl) -1-phenyl-1H-benzo [ d)]Imidazole) acetylacetonatoiridium (III) (abbreviation (fbi) 2 Ir (acac)), tris (2-phenylpyridine) iridium (III) (Ir (ppy) for short) 3 ) Or tris [2- (4-n-hexylphenyl) quinoline]Iridium (III) (Ir (hpiq) for short) 3 ) The structural formulas are respectively as follows:
the hole type organic main body material is 4,4', 4' -tri (carbazole-9-yl) triphenylamine (TCTA for short), 4,4', -N, N' -dicarbazolyl-biphenyl or tris [4- (9-phenylfluorene) phenyl ] amine (TFTPA for short), and the structural formulas are respectively as follows:
the electron-dominated light-emitting layer comprises the rare earth complex of claim 1, an organic light-emitting material, and an electron-type organic host material, wherein the organic light-emitting material is Preferably (PQ) 2 Ir(dpm)、Ir(mppy) 3 Bis (4,6-difluorophenylpyridine-N, C2) picolinoyl iridium (FIrpic for short), ir (ppy) 3 Or Ir (hpiq) 3 FIrpic has the following structural formula:
the electronic organic main body material is 2,6-di [3- (9H-9-carbazolyl) phenyl]Pyridine (26 DCzPPy for short), 9- (4-tert-butylphenyl) -3,6-bis (triphenylsilyl) -9H-carbazole (CzSi for short), tris (8-hydroxyquinoline) aluminum (III) (Alq 3 for short) or 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI for short) and the structural formulas are respectively as follows:
the hole transport layer is a bipyrazino [2,3-f:2',3' -h ] quinoxaline-2,3,6,7, 10, 11-hexanenitrile (abbreviated as HAT-CN), 4,4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), N' -diphenyl-N, N '-bis (1-naphthyl) (1,1' -diphenyl) -4,4 '-diamine (abbreviated as NPB) and 4,4',4 ″ -tris [ phenyl (m-tolyl) amino ] triphenylamine (abbreviated as m-MTDATA), and the molecular structural formulas of HAT-CN and TAPC are as follows:
the electron transport layer/hole blocking layer is 1,3,5-tris (6- (3- (pyridin-3-yl) phenyl) pyridin-2-yl) benzene (Tm 3PyP26PyB for short), 1,3,5-tris- (3-pyridyl-3-phenyl) benzene (TmPyPB for short) or 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1,2,4-triazocene (TAZ for short), and the molecular structural formula is as follows:
the first electrode comprises an anode layer and an anode modification layer, wherein the anode layer is made of ITO glass with an electrode, and the anode modification layer is HAT-CN.
The second electrode is a cathode layer and a cathode modification layer, the cathode layer is preferably Al metal, and the cathode modification layer is preferably LiF.
In some possible implementations, OLEDs include an anode layer, an anode modification layer, a hole transport layer, a hole dominated light emitting layer, an electron transport layer/hole blocking layer, a cathode modification layer, and a cathode layer. The preparation of OLEDs is as follows:
firstly, pretreating the anode layer 2, preferably alternately cleaning with special glass washing liquor and tap water, and then carrying out ultrasonic treatment and drying; at less than 1.0X 10 -5 And (3) evaporating an anode modification layer, a hole transport layer, a hole leading light emitting layer, an electron transport layer/hole blocking layer, a cathode modification layer and a cathode layer on the anode layer in sequence under the vacuum degree of Pa. The structure of the OLED device is shown in fig. 1, where 1 is a substrate, 2 is an anode layer, 3 is an anode modification layer, 4 is a hole transport layer, 5 is a hole-dominant light-emitting layer, 6 is an electron-dominant light-emitting layer, 7 is an electron transport layer/hole blocking layer, 8 is a cathode modification layer, and 9 is a cathode layer.
The thickness of the cathode modification layer 3 is 7-9 nm, preferably 8nm, and the evaporation speed is less than or equal to 0.01nm/s; the thickness of the hole transport layer 4 is 48-52 nm, preferably 50nm, and the evaporation speed is less than or equal to 0.05nm/s; the thickness of the hole-leading luminescent layer 5 is 9-11 nm, preferably 10nm, wherein the content of the organic luminescent material is 1-10 wt%, preferably 3wt%, 4wt% or 8wt%, the evaporation rate of the organic luminescent material is less than or equal to 0.004nm/s, and the evaporation rate of the hole-type organic host material is less than or equal to 0.05nm/s; the thickness of the electron-dominant luminescent layer 6 is 9-11 nm, preferably 10nm, wherein the content of the rare earth complex is 0.1-1.0 10wt%, preferably 0.4wt%, the content of the organic luminescent material is 1-20 wt%, preferably 4wt%, 8wt% or 16wt%, the evaporation rate of the rare earth complex is less than or equal to 0.0002nm/s, the evaporation rate of the organic luminescent material is less than or equal to 0.004nm/s, and the evaporation rate of the electronic organic host material is less than or equal to 0.05nm/s; the thickness of the electron transport layer/hole blocking layer 7 is 58-62 nm, preferably 60nm, and the evaporation speed is less than or equal to 0.05nm/s; the thickness of the cathode modification layer 8 is 0.08-1.02 nm, preferably 1nm, and the evaporation speed is less than or equal to 0.005nm/s; the cathode layer 9 has a thickness of 95 to 105nm, preferably 100nm, and an evaporation rate of 0.5nm/s or less.
And (3) carrying out performance test on the prepared OLEDs under the drive of direct-current voltage, wherein the performance test comprises a starting voltage, maximum brightness, maximum current efficiency, maximum power efficiency and color coordinates. Experimental results show that the rare earth complex [ Gd (DPPDA) 2] (TOA) provided by the invention can be used for sensitizing OLEDs.
Example 1: laboratory Synthesis of [ Gd (DPPDA) 2] (TOA)
Under the nitrogen environment, 0.93g of bathocuproine and 1.35g of selenium dioxide are added into a mixed solvent of 46mL of dioxane and 2mL of deionized water, the mixture is heated and refluxed for reaction for 3h at the temperature of 105 ℃, the mixture is cooled to room temperature after the reaction is finished, the solvent is evaporated under reduced pressure, 40mL of 48 percent nitric acid solution is added into the residual residue, the mixture is continuously heated and refluxed for reaction for 3h at the temperature of 105 ℃, the reaction mixture is cooled to the room temperature after the reaction, the reaction mixture is poured onto crushed ice, bright yellow solid is observed to be separated out, the mixture is filtered, the mixture is sequentially washed to be neutral by deionized water and glacial acetonitrile, the obtained solid is heated and dried under vacuum at the temperature of 60 ℃, and 0.92g of ligand is obtained.
Adding the obtained ligand into 20mL of ethanol, dropwise adding 4mL of trioctylamine, after the ligand is completely dissolved, dropwise adding 30mL of ethanol solution in which 0.28g of gadolinium chloride is dissolved within half an hour, stirring and reacting for 4 hours at room temperature to obtain light yellow precipitate, filtering the light yellow precipitate, washing with ethanol for three times, and heating and drying under vacuum at the temperature of 60 ℃ to obtain 1g of crude product. The crude product obtained was purified at room temperature using a volume of 1:1, recrystallizing the mixed solvent of ethanol and dichloromethane to obtain the rare earth gadolinium complex [ Gd (DPPDA) 2 ](TOA), the complex being a brownish yellow crystal.
Example 2: [ Gd (DPPDA) 2 ](TOA) Pilot Synthesis
Under the nitrogen environment, 93g of bathocuproine, 135g of selenium dioxide, 4.6L of dioxane and 200mL of deionized water are sequentially added into a distillation flask with the capacity of 10L, fully stirred by a cantilever type constant-speed electric stirrer, then placed into a large-caliber oil bath kettle, heated and refluxed for reaction for 12 hours at the temperature of 105 ℃, cooled to room temperature after reaction, decompressed and evaporated to remove the solvent, a small amount of 4L of 48% nitric acid solution is added into the residual residue for multiple times, and heated, stirred and refluxed for reaction for 12 hours at the temperature of 105 ℃. After the reaction system was cooled to room temperature, the reaction mixture was slowly poured onto crushed ice with constant stirring, a bright yellow solid was observed to precipitate, filtered, washed sequentially with deionized water and glacial acetonitrile to neutrality, and the resulting solid was dried under vacuum at 60 ℃ to obtain 90g of ligand.
Mixing the obtained ligand and 2L ethanol in a 10L round-bottom flask, fully stirring by using a cantilever type constant-speed stirrer, dropwise adding 400mL (excessive) of trioctylamine into the mixed system at the speed of 10mL/min under stirring, completely dissolving the ligand, adding 3L of an ethanol solution dissolved with 28g of gadolinium chloride into the mixed system at the speed of 10mL/min within half an hour (the preparation method of the ethanol solution of gadolinium chloride is that the ethanol solution is slowly added into gadolinium chloride powder and is continuously stirred, the solution temperature is kept below 30 ℃ all the time), stirring and reacting for 12h at room temperature to obtain a light yellow precipitate, filtering the light yellow precipitate, washing for three times by using ethanol, and heating and drying under vacuum to obtain 100g of a crude product. Dissolving the crude product with 200mL dichloromethane at room temperature, adding 200mL ethanol, transferring into 1L distillation flask, slowly heating and evaporating at 40 deg.C in oil bath pan to precipitate brown yellow crystal, filtering, and vacuum heating and drying at 60 deg.C to obtain rare earth gadolinium complex [ Gd (DPPDA) 2 ](TOA)。
Example 3: [ Gd (DPPDA) 2 ]Batch Synthesis of (TOA)
The equipment and pipelines required by the process route are made of glass or thick polytetrafluoroethylene materials, and metal or alloy materials cannot be used.
Injecting 147L of dioxane and 6.4L of deionized water into a 500L glass-lined reaction tank, setting the stirring speed of a stirrer to be 50r/min, then slowly adding 3kg of copper bath agent and 4.3kg of selenium dioxide into the reaction tank, setting the rotating speed to be 100r/min, butting a cooling tower, starting circulating cooling water, heating to 105 ℃ at the speed of 10 ℃/h, reacting at 105 ℃ for 24h, stopping heating after the reaction, cooling to 35 ℃ at the speed of 10 ℃/h, setting the rotating speed to be 50r/min, connecting a cold trap of the reaction tank cooled by liquid nitrogen with a mechanical vacuum pump, pre-pumping the reaction tank for 5h at the speed of 10KPa/h by the mechanical vacuum pump, continuously pumping the reaction tank at the speed of 5KPa/h until all the solvent in the reaction tank is melted, and recovering and distilling the solvent in the cold trap after the solvent is recovered to room temperature. (whether peroxide is generated in the mixed solvent obtained by recycling needs to be checked, and the specific method is that 2-3 drops of concentrated sulfuric acid, 1mL of 2% potassium iodide solution and 1-2 drops of starch solution are added into the mixed solvent obtained by recycling, 1mL of evaporated solvent is added after uniform mixing, and the existence of peroxide is indicated when blue color appears, and the solvent can not be recycled any more at this moment). Then, adjusting the rotation speed to 50r/min, adding 128L 48% nitric acid solution into a reaction tank, connecting the reaction tank with a cooling tower and a denitration tower, starting circulating water, setting the rotation speed to 100r/min, setting the temperature to be increased to 105 ℃ at the speed of 10 ℃/h, continuously reacting for 24h, stopping heating after the reaction, and cooling to the room temperature at the speed of 10 ℃/h. And slowly introducing the reaction liquid in the reaction tank into a continuously stirred glass-lined tank filled with crushed ice at the speed of 1mL/s (the crushed ice is supplemented in time when the liquid surface of the glass-lined tank is over the crushed ice), introducing the reaction liquid into a rotary vacuum filter for filtering after the crushed ice is completely melted, washing with water and acetonitrile for three times respectively after the filtering is finished, and then drying, blowing loose and discharging cakes to obtain 2.8kg of ligand.
Injecting 64L of ethanol into a glass-lined reaction tank, setting the stirring speed of a stirrer to be 50r/min, then slowly adding the obtained ligand into the reaction tank, setting the rotating speed to be 100r/min, adding 13L (excessive) of trioctylamine at the speed of 10mL/s, and reacting for 12 hours under stirring; then, slowly adding 900g of gadolinium chloride solid powder, and continuously stirring for reaction for 24 hours; and (3) introducing the mixed solution obtained by the reaction into a rotary drum vacuum filter for filtering, washing the filtered mixed solution with ethanol for three times, and then blowing the filtered mixed solution for loosening and discharging cakes to obtain a crude product of 3kg. Adding the obtained crude product into a 100L enamel reaction tank, dissolving with 6L dichloromethane, adding 6L ethanol, evaporating at 40 deg.C, collecting and recovering the evaporated solvent via cold trap, stopping evaporation when a large amount of brown yellow crystals appear in the tank, filtering, washing with ethanol, and vacuum heating and drying at 60 deg.C to obtain rare earth gadolinium complex [ Gd (DPPDA) 2 ](TOA)。
For the rare earth gadolinium complex [ Gd (DPPDA) prepared by the invention 2 ](TOA) is shown in FIG. 2, and FIG. 2 is a thermogravimetric analysis curve, and it can be seen from FIG. 2 that the complex has good performance at 300 deg.CThermal stability of (2).
For the prepared rare earth gadolinium complex [ Gd (DPPDA) 2 ](TOA) the results of low-temperature phosphorescence measurements are shown in FIG. 3, and FIG. 3 is a low-temperature phosphorescence spectrum, as shown in FIG. 3, [ Gd (DPPDA) 2 ]The triplet energy level of (TOA) is 2.44eV, and the triplet energy level is between the triplet energy level of the host material and the triplet energy level of the luminescent material, so that the organic electroluminescent device can be used as an energy step in an OLED luminescent layer, the energy transfer from the host material to the luminescent material is promoted, and the utilization rate of excitons is improved.
For the prepared rare earth gadolinium complex [ Gd (DPPDA) 2 ](TOA) the ultraviolet-visible absorption spectrum was analyzed, and the results are shown in FIG. 4, and FIG. 4 is an ultraviolet-visible absorption spectrum, from which FIG. 4 shows that [ Gd (DPPDA) 2 ](TOA) has a maximum absorption wavelength in the ultraviolet visible region of 375nm, meaning [ Gd (DPPDA) ] 2 ]The energy gap between the HOMO level and the LUMO level of (TOA) was 3.31eV. The larger energy gap is beneficial to balancing the carrier distribution of OLEDs, and the electroluminescent performance of the device is improved.
Example 4: [ Gd (DPPDA) 2] (TOA) for sensitizing Red OLEDs
The ITO glass with the strip-shaped electrodes is sequentially and alternately cleaned by special glass lotion and tap water, then is subjected to ultrasonic treatment for 15min by using deionized water, and then is placed into an oven for drying, and the dried ITO glass is transferred to an organic evaporation chamber through a pretreatment vacuum chamber. At less than 1.0X 10 -5 And under the vacuum degree of Pa, sequentially evaporating an HAT-CN anode modification layer 3 with the thickness of 8nm and HAT-CN with the thickness of 40nm (0.3 wt%) on the ITO layer: TAPC with a 10nm thick TAPC hole transport layer 4, 10nm thick (PQ) 2 Ir (dpm) and TCTA doped hole-dominated luminescent layer 5, 10nm thick [ Gd (DPPDA) ] 2 ](TOA) and (PQ) 2 Ir (dpm) co-doped 26DCzPPy electron dominates Tm of the light emitting layer 6, 60nm thick 3 PyP 26 PyB electron transport layer/hole blocking layer 7; then transferring the substrate to a metal evaporation chamber at a temperature of less than 1.0 × 10- 6 Evaporating a LiF cathode modification layer 8 with the thickness of 1nm under the vacuum degree of Pa, and finally evaporating an Al metal cathode layer 9 with the thickness of 100nm on the LiF layer through a special mask to prepare the ITO/HAT-CN (8 nm)/HAT-CN (0.3 wt%): TAPC (40 nm)/TAPC (10 nm)/(PQ) 2 Ir(dpm)(4wt％):TCTA(10nm)/[Gd(DPPDA) 2 ](TOA)(0.4wt％):(PQ) 2 Ir(dpm)(4wt％):26DCzPPy(10nm)/Tm 3 PyP 26 PyB (60 nm)/LiF (1 nm)/Al (100 nm) red OLEDs.
The evaporation rate of the anode modification layer 3HAT-CN is controlled at 0.01nm/s, the evaporation rate of TAPC in the hole transport layer 4 is controlled at 0.05nm/s, and the hole leads to the luminescent layer 5 (PQ) 2 The evaporation rates of Ir (dpm) and TCTA are respectively controlled at 0.002nm/s and 0.05nm/s, and the electron dominates the luminescent layer 6 [ Gd (DPPDA) 2 ](TOA) the evaporation rate was controlled at 0.0002nm/s, (PQ) 2 The evaporation rates of Ir (dpm) and 26DCzPPy are respectively controlled at 0.002nm/s and 0.05nm/s, the evaporation rate of Tm3PyP26PyB in the electron transport layer/hole barrier layer 7 is controlled at 0.05nm/s, the evaporation rate of LiF in the cathode modification layer 8 is controlled at 0.005nm/s, and the evaporation rate of Al in the metal cathode layer 9 is controlled at 0.5nm/s.
Driven by DC voltage, for [ Gd (DPPDA) 2 ](TOA) sensitized red light OLEDs are subjected to performance test, and the test result is that the starting voltage of a sensitized device is 3.2V and is lower than the starting voltage (3.3V) of an unsensitized device; the maximum brightness of the sensitization device is 77835cd/m 2 Higher than the maximum luminance of an unsensitized device (61448 cd/m) 2 ) (ii) a The maximum current efficiency of the sensitized device is 67.68cd/A, which is higher than that of the unsensitized device (52.83 cd/A); the maximum power efficiency of the sensitized device is 53.15lm/W, which is higher than that of the unsensitized device (42.56 lm/W); the color coordinate of the sensitized device is (0.604,0.395), and the color coordinate of the unsensitized device is (0.603,0.395); FIG. 5 shows red OLEDs at a luminance of 20000cd/m 2 As can be seen from FIG. 5, the main peaks of the spectra of the Mihua device and the unsensitized device were at 595nm. The test result shows that [ Gd (DPPDA) 2 ](TOA) can be used to sensitize red OLEDs.
Example 5: [ Gd (DPPDA) 2 ](TOA) for sensitizing Green OLEDs
Firstly, sequentially and alternately cleaning ITO glass with strip-shaped electrodes by using special glass lotion and tap water, then placing the ITO glass into an oven for drying after carrying out ultrasonic treatment for 15 minutes by using deionized water, and then transferring the dried ITO glass into a pretreatment vacuum chamberAnd moving to an organic evaporation chamber. At less than 1.0X 10 -5 And under the vacuum degree of Pa, sequentially evaporating an HAT-CN anode modification layer 3 with the thickness of 8nm and HAT-CN with the thickness of 40nm (0.3 wt%) on the ITO layer: TAPC with a 10nm thick TAPC hole transport layer 4, 10nm thick Ir (mppy) 3 Hole-dominant emitting layer 5 doped with TCTA 10nm thick [ Gd (DPPDA) 2 ](TOA) and Ir (mppy) 3 Co-doped CzSi electron dominates the Tm of the light emitting layer 6, 60nm thick 3 PyP 26 PyB hole blocking layer 7, and then the substrate was transferred to a metal evaporation chamber at less than 1.0 × 10 -6 Evaporating a LiF cathode modification layer 8 with the thickness of 1nm under the vacuum degree of Pa, and finally evaporating an Al metal cathode layer 9 with the thickness of 100nm on the LiF layer through a special mask to prepare the ITO/HAT-CN (8 nm)/HAT-CN (0.3 wt%): TAPC (40 nm)/TAPC (10 nm)/Ir (mppy) 3 (8wt％):TCTA(10nm)/[Gd(DPPDA) 2 ](TOA)(0.4wt％):Ir(mppy) 3 (8wt％):CzSi(10nm)/Tm 3 PyP 26 PyB (60 nm)/LiF (1 nm)/Al (100 nm) green OLEDs.
The evaporation rate of the anode modification layer 3HAT-CN is controlled at 0.01nm/s, the evaporation rate of TAPC in the hole transport layer 4 is controlled at 0.05nm/s, and Ir (mppy) in the hole-leading luminescent layer 5 3 And the evaporation rates of TCTA are controlled at 0.004nm/s and 0.05nm/s, respectively, and electrons dominate [ Gd (DPPDA) in the light-emitting layer 6 2 ](TOA) Evaporation Rate controlled at 0.0002nm/s, ir (mppy) 3 And the evaporation rates of CzSi are respectively controlled at 0.004nm/s and 0.05nm/s, and Tm is in the electron transport layer/hole blocking layer 7 3 PyP 26 The evaporation rate of PyB is controlled at 0.05nm/s, the evaporation rate of LiF in the cathode modification layer 8 is controlled at 0.005nm/s, and the evaporation rate of Al in the metal cathode layer 9 is controlled at 0.5nm/s.
Driven by DC voltage, for [ Gd (DPPDA) 2 ]The performance test of the green light OLEDs (organic electroluminescent devices) sensitized by (TOA) shows that the brightening voltage of the sensitized devices is 3.1V and is lower than that of the non-sensitized devices (3.2V); the maximum brightness of the sensitized device is 61805cd/m 2 Higher than the maximum luminance of an unsensitized device (52935 cd/m) 2 ) (ii) a The maximum current efficiency of the sensitized device is 85.92cd/A, which is higher than the maximum current efficiency (68.70 cd/A) of the unsensitized device; maximum power efficiency of the sensitized device is77.13lm/W, which is higher than the maximum power efficiency (58.33 lm/W) of the unsensitized device; the color coordinate of the sensitized device is (0.304,0.626), the color coordinate of the unsensitized device is (0.309,0.623); FIG. 6 shows sensitized and non-sensitized devices at a luminance of 20000cd/m 2 As seen from FIG. 6, the main peaks of the spectra of the sensitized device and the unsensitized device were 514nm. The test result shows that [ Gd (DPPDA) ]provided by the invention 2 ](TOA) can be used to sensitize green OLEDs.
Example 6: [ Gd (DPPDA) 2 ](TOA) for sensitizing white light
The ITO glass with the strip-shaped electrodes is sequentially and alternately cleaned by special glass lotion and tap water, then is placed into an oven for drying after being subjected to ultrasonic treatment for 15 minutes by deionized water, and then the dried ITO glass is transferred to an organic evaporation chamber through a pretreatment vacuum chamber. At less than 1.0X 10 -5 And under the vacuum degree of Pa, sequentially evaporating an HAT-CN anode modification layer 3 with the thickness of 8nm and HAT-CN with the thickness of 40nm (0.3 wt%) on the ITO layer: TAPC with a 10nm thick TAPC hole transport layer 4, 10nm thick (fbi) 2 Ir (acac) and TCTA doped hole-dominated light emitting layer 5, 10nm thick [ Gd (DPPDA) ] 2 ](TOA) and FIrpic codoped CZSi electron dominates the Tm of the light emitting layer 6, 60nm thick 3 PyP 26 PyB electron transport layer/hole blocking layer 7. The substrate is then transferred to a metal evaporation chamber at less than 1.0 x 10 -6 Evaporating a 1 nm-thick LiF cathode modification layer 8 under Pa vacuum degree, and finally evaporating a 100 nm-thick Al metal cathode layer 9 on the LiF layer through a special mask to prepare the ITO/HAT-CN (8 nm)/HAT-CN (0.3 wt%): TAPC (40 nm)/TAPC (10 nm)/(fbi) 2 Ir(acac)(3wt％):TCTA(10nm)/[Gd(DPPDA) 2 ](TOA)(0.4wt％):FIrpic(16wt％):CzSi(10nm)/Tm 3 PyP 26 PyB (60 nm)/LiF (1 nm)/Al (100 nm) white light OLEDs.
The evaporation rate of the anode modification layer 3HAT-CN is controlled at 0.01nm/s, the evaporation rate of TAPC in the hole transport layer 4 is controlled at 0.05nm/s, and holes lead the luminescent layer 5 (fbi) 2 The evaporation rates of Ir (acac) and TCTA are controlled at 0.0015nm/s and 0.05nm/s, respectively, and the electron dominates the luminescent layer 6 [ Gd (DPPDA) 2 ](TOA) the evaporation rate was controlled at 0.0002nm/s, FIrpic and CzSiTm in the hole-blocking layer 7 is controlled to be 0.008nm/s and 0.05nm/s, respectively 3 PyP 26 The evaporation rate of PyB is controlled at 0.05nm/s, the evaporation rate of LiF in the cathode modification layer 8 is controlled at 0.005nm/s, and the evaporation rate of Al in the metal cathode layer 9 is controlled at 0.5nm/s.
Driven by DC voltage, for [ Gd (DPPDA) 2 ](TOA) sensitized white light OLEDs (organic light emitting diodes) are subjected to performance test, and the test result is that the brightening voltage of a sensitized device is 2.7V and is lower than the brightening voltage (3.0V) of an unsensitized device; the maximum brightness of the sensitized device is 32865cd/m2, which is higher than the maximum brightness of the unsensitized device (25367 cd/m 2); the maximum current efficiency of the sensitized device is 67.15cd/A, which is higher than that of the unsensitized device (62.96 cd/A); the maximum power efficiency of the sensitized device is 65.72lm/W, which is higher than that of the unsensitized device (50.69 lm/W); the sensitized device has a color coordinate of (0.282,0.400) and the unsensitized device has a color coordinate of (0.381,0.417).
FIG. 7 is a graph showing electroluminescence spectra of a sensitized device and an unsensitized device at a current density of 10mA, and it can be seen from FIG. 7 that main peaks of the spectra of the sensitized device and the unsensitized device are at 473nm, 494nm, 562nm and 607nm, respectively. FIG. 8 shows [ Gd (DPPDA) 2] provided by the present invention]The voltage-current density-luminance characteristic curve of (TOA) sensitized white light OLEDs (OLEDs) shows that the luminance of the device increases with the increase of the current density and the driving voltage, wherein the turn-on voltage of the sensitized device is 2.7V, and the maximum luminance is 32865cd/m 2 . FIG. 9 shows [ Gd (DPPDA) ] provided by the present invention 2 ](TOA) sensitized white light OLEDs current density-power efficiency-current efficiency characteristic curve, wherein the maximum current efficiency of the sensitized device is 67.15cd/A, and the maximum power efficiency is 62.96lm/W. The test result shows that [ Gd (DPPDA) 2 ](TOA) can be used to sensitize white light OLEDs.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A rare earth complex having the structure of formula (I):
2. an organic electroluminescent device comprising: a first electrode, a second electrode, and a light-emitting layer disposed between the first electrode and the second electrode, the light-emitting layer comprising the rare earth complex of claim 1 and a light-emitting material.
3. The organic electroluminescent device according to claim 2, wherein the light emitting layer comprises a hole-dominant light emitting layer and an electron-dominant light emitting layer, and the electron-dominant light emitting layer comprises the rare earth complex according to claim 1.
4. The organic electroluminescent device according to claim 3, wherein the rare earth complex is contained in the electron-dominant light-emitting layer in an amount of 0.1 to 1.0wt%, and the light-emitting material is contained in the electron-dominant light-emitting layer in an amount of 1 to 20wt%.
5. The organic electroluminescent device of claim 4, further comprising optionally the following structure:
a hole transport layer disposed between the first electrode and the hole-dominant emission layer;
an electron transport layer disposed between the second electrode and the electron-dominated light-emitting layer.
6. The organic electroluminescent device of claim 5, further comprising optionally the following structure:
an electron blocking layer disposed between the hole transport layer and the hole-dominant emission layer;
a hole blocking layer disposed between the electron transport layer and the electron dominated light emitting layer.
7. An organic electroluminescent device as claimed in any one of claims 3 to 6, wherein the hole-dominant emissive layer comprises an organic emissive material and a hole-type organic host material, the organic emissive material being [ bis (2-phenylquinoline) ] (2,2,6,6-tetramethylheptane-3,5-heptanedionic acid) iridium (III), tris [2- (p-tolyl) pyridinium ] iridium (III), bis (2- (9,9-diethyl-fluoren-2-yl) -1-phenyl-1H-benzo [ d ] imidazole) iridium (III) acetylacetonate, tris (2-phenylpyridinium) iridium (III) or tris [2- (4-N-hexylphenyl) quinoline ] iridium (III), the hole-type organic host material being 4,4',4 "-tris (carbazol-9-yl) triphenylamine, 4,4', -N, N ' -dicarbazolyl-biphenyl or tris [4- (9-phenyl) phenyl ] amine.
8. The organic electroluminescent device according to any one of claims 3 to 6, wherein the electron-dominant light-emitting layer comprises the rare earth complex, the organic light-emitting material and the electronic organic host material as described in claim 1, and the organic light-emitting material is [ bis (2-phenylquinoline) ] (2,2,6,6-tetramethylheptane-3,5-heptanedionate) iridium (III), tris [2- (p-tolyl) pyridine ] iridium (III), bis (4,6-difluorophenylpyridine-N, C2) picolinoyl iridium, tris (2-phenylpyridine) iridium (III) or tris [2- (4-N-hexylphenyl) quinoline ] iridium (III); the electronic organic host material is 2,6-bis [3- (9H-9-carbazolyl) phenyl ] pyridine, 9- (4-tert-butylphenyl) -3,6-bis (triphenylsilyl) -9H-carbazole, tris (8-hydroxyquinoline) aluminum (III) or 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene.
9. The organic electroluminescent device according to claim 6, wherein the hole transport layer is a bipyrazino [2,3-f:2',3' -H ] quinoxaline-2,3,6,7,10,11-hexanenitrile, 4,4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], N' -diphenyl-N, N '-bis (1-naphthyl) (1,1' -diphenyl) -4,4 '-diamine, and 4,4',4 "-tris [ phenyl (m-tolyl) amino ] triphenylamine, the electron transport layer/hole barrier layer being one or more of 1,3,5-tris (6- (3- (pyridin-3-yl) phenyl) pyridin-2-yl) benzene, 1,3,5-tris- (3-pyridyl-3-phenyl) benzene, or 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1,2,4-triazene 343425.
10. The organic electroluminescent device according to any one of claims 3 to 6, wherein the first electrode comprises an anode layer and an anode modification layer, the anode layer is ITO glass with an electrode, and the anode modification layer is dipyrazino [2,3-f:2',3' -h ] quinoxaline-2,3,6,7, 10, 11-hexanenitrile, the second electrode is a cathode layer and a cathode modification layer, the cathode layer is Al metal, and the cathode modification layer is LiF.
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| US20180248138A1 (en) * | 2014-10-30 | 2018-08-30 | Changchun Institute Of Applied Chemistry, Chinese Academy Of Sciences | White organic electroluminescent device and preparation method thereof |
| CN110950861A (en) * | 2019-11-01 | 2020-04-03 | 广西师范大学 | Mononuclear dysprosium complex with 1, 10-phenanthroline-2, 9-dicarboxylic acid as ligand and preparation method and application thereof |
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| US20180248138A1 (en) * | 2014-10-30 | 2018-08-30 | Changchun Institute Of Applied Chemistry, Chinese Academy Of Sciences | White organic electroluminescent device and preparation method thereof |
| CN110950861A (en) * | 2019-11-01 | 2020-04-03 | 广西师范大学 | Mononuclear dysprosium complex with 1, 10-phenanthroline-2, 9-dicarboxylic acid as ligand and preparation method and application thereof |
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