CN108250214B - Oxaspirofluorene triphenylamine derivative, preparation method and application thereof - Google Patents

Oxaspirofluorene triphenylamine derivative, preparation method and application thereof Download PDF

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CN108250214B
CN108250214B CN201810004552.8A CN201810004552A CN108250214B CN 108250214 B CN108250214 B CN 108250214B CN 201810004552 A CN201810004552 A CN 201810004552A CN 108250214 B CN108250214 B CN 108250214B
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廖良生
蒋佐权
王亚坤
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Suzhou Jiuxian New Material Co ltd
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Abstract

The invention discloses an oxaspirofluorene triphenylamine derivative, a preparation method and application thereof. By effectively controlling the rigidity, the conjugation degree and the electron-withdrawing strength of the main material structure, the singlet state-triplet state energy level difference of the material can be accurately regulated and controlled to be reduced, and the turn-on voltage of the device is obviously reduced. In addition, the material of the invention has excellent resonance energy transfer performance. Compared with the common phosphorescent host material, the performance and the efficiency roll-off of the device are qualitatively improved. In addition, the power efficiency can still reach the highest efficiency (58 lumens per watt) based on the material under the condition of doping with very low guest concentration (0.5 wt%). This result is an instructive effect of reducing the manufacturing cost of the organic phosphorescent light emitting diode by using the reduced concentration.

Description

Oxaspirofluorene triphenylamine derivative, preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an oxaspirofluorene triphenylamine derivative, a preparation method and application thereof.
Background
Organic electroluminescence is a self-light emitting device in which electrons injected from a cathode (first electrode) and holes injected from an anode (second electrode) are recombined at a light emitting center to form a molecular exciton by sandwiching a light emitting layer between a pair of electrodes and applying a voltage, and the molecular exciton releases energy when returning to a ground state to emit light. The organic electroluminescent device has the characteristics of low voltage, high brightness, good color purity, wide visual angle, quick response, good temperature adaptability and the like, and is widely applied to electronic product displays such as computers, mobile phones, MP3, televisions and the like. Organic electroluminescent materials are generally classified into singlet fluorescent dyes and triplet phosphorescent dyes, wherein singlet fluorescence can only utilize 25% of excitons due to transition selection rule, the remaining 75% of excitons are lost in a thermal form or other non-radiative manner, whereas triplet phosphorescent light emission can utilize 100% of excitons due to heavy atom effect, so that the light emission efficiency is far higher than that of singlet fluorescent light emission. Therefore, in the existing organic electroluminescent devices, a host-guest doped structure is mostly adopted, that is, fluorescent dyes or phosphorescent dyes are dispersed in host substances at a certain concentration, so that concentration quenching and triplet-triplet annihilation are avoided, and the device performance is improved.
Among the RGB (red-green-blue) color system, red OLEDs are of particularly great interest. This is mainly due to the fact that in optics, red has the longest wavelength in the spectrum of visible light, which means that scattering of light is minimal and therefore can be seen from a greater distance than other hues. In addition, red can increase our sense of danger, and thus is widely used as a striking warning sign. For example, automobile manufacturers like audi and bmw have announced plans for their light technology using red OLEDs as tail lights. In addition, since organic materials can be deposited or printed on a 3-D substrate having any shape, a backlight driving is not required, and there is little work dissipation in the process. Although promising, organic phosphorescent devices typically require high guest doping concentrations to achieve high brightness requirements. The high concentration inevitably causes an increase in the cost of the organic phosphorescent device. Any realization of high luminance efficiency while reducing the cost of the device remains a troublesome problem.
Disclosure of Invention
The invention aims to provide a novel material (small singlet-triplet difference, effective resonance energy transfer and the like) which can be still normally used under low guest doping concentration or can realize higher efficiency under low guest doping concentration. To solve the problem of reducing the cost of the organic phosphorescent device.
In order to achieve the purpose, the invention provides the following technical scheme:
an oxaspirofluorene triphenylamine derivative has a chemical structure shown in a formula (I):
Figure BDA0001538184970000021
wherein the main body is oxaspirofluorene triphenylamine, and the substituents R1-R8 are respectively and independently selected from hydrogen, cyano, bis (trimethylphenyl) boron fluoride, 2-azapyridine, 3-azapyridine and 2, 4-diphenyl-1, 3, 5-triazine.
Preferably, the oxaspirofluorene triphenylamine derivative comprises a derivative of the following formulae ii to ix:
(1) the substituent R2 is cyano, the substituents R1, R3-R8 are hydrogen, the name is OSTFP1, and the structural formula is shown as the formula (II)
Shown in the figure:
Figure BDA0001538184970000022
(2) the substituent R2 is bis (trimethylphenyl) boron fluoride, the substituents R1 and R3-R8 are hydrogen, the name is OSTFP2, and the structure is shown as the formula (III):
Figure BDA0001538184970000031
(3) the substituent R3 is 2-azapyridine, the substituents R1-R2 and R4-R8 are hydrogen, the name is OSTFP3, and the structural formula is shown as the formula (IV)
Figure BDA0001538184970000032
(4) The substituent R5 is 3-azapyridine, the substituents R1-R4 and R6-R8 are hydrogen, the name is OSTFP4, and the structural formula is shown as the formula (V):
Figure BDA0001538184970000033
(5) the substituent R8 is 2, 4-diphenyl-1, 3, 5-triazine, the substituent R1-R7 is hydrogen, the name is OSTFP5, and the structural formula is shown as the formula (VI):
Figure BDA0001538184970000034
(6) the substituent R2 is cyano, R6 is 2-azapyridine, and the substituents R1-R3, R5 and R7-R8 are hydrogen, are named OSTFP6, and have the structural formula shown in the formula (VII):
Figure BDA0001538184970000041
(7) the substituent R2 is cyano, R4 is 3-azapyridine, and the substituents R2-R3 and R5-R8 are hydrogen, are named OSTFP7, and have the structural formula shown in the formula (VIII):
Figure BDA0001538184970000042
(8) the substituent R3 is 3-azapyridine, R7 is cyano, R1-R2, R4-R6 and R8 substituents are hydrogen, the name is OSTFP8, and the structural formula is shown as the formula (IX):
Figure BDA0001538184970000043
the invention relates to application of an oxaspirofluorene triphenylamine derivative in an organic electroluminescent red phosphorescent device.
The invention also provides an organic electroluminescent red phosphorescent device containing the host material of the oxacyclo spirofluorene triphenylamine derivative, which comprises glass, a conductive glass substrate layer attached to the glass, a hole injection layer attached to the conductive glass substrate layer, a hole transport layer attached to the hole injection layer, a luminescent layer attached to the hole transport layer, a hole blocking layer attached to the luminescent layer, an electron transport layer attached to the hole blocking layer, and a cathode layer attached to the electron transport layer, wherein the luminescent layer is composed of the host material and an object material, the host material is a derivative of the structure shown in the formula (I), and the object material is an iridium complex with a ring metal ligand.
Preferably, the iridium complex is red-emitting acetylacetone bis (2-methyl dibenzo [ F, H)]Quinoxaline) Iridium (Ir (MDQ)2(acac))。
Further, the doping concentration of the guest material is not higher than 2.0 wt%.
The preparation method of the organic electroluminescent red phosphorescent device comprises the following steps:
(1) pretreating an ITO transparent conductive glass substrate;
(2) vacuum evaporating a hole injection layer on the ITO conductive glass;
(3) vacuum evaporating a hole transport layer and an electron blocking layer on the hole injection layer;
(4) adopting a double-source evaporation process, taking the oxaspirofluorene triphenylamine derivative as a host material and the red light iridium complex with a ring metal ligand as an organic light-emitting layer of a guest material, and carrying out vacuum evaporation on a hole blocking layer and an electron transport layer on the organic light-emitting layer;
(5) and vacuum evaporating a cathode layer on the electron transport layer.
Further, the hole injection layer is molybdenum trioxide or 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene, and the hole transport layer is N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 4-N, N ' -dicarbazolylbiphenyl or 1,1' -bis-4, 4' -dimethyltriphenylamine cyclohexane; the electron transport layer is 1,3, 5-tri (N-phenyl-2-benzimidazole-2) benzene, 4, 7-diphenyl-1, 10-phenanthroline or 4, 6-bis (3, 5-di (4-pyridine) phenyl) -2-methylpyrimidine; the cathode layer is Liq and Al.
Further, the evaporation rate of the hole injection layer is
Figure BDA0001538184970000051
The evaporation rate of the hole transport layer and the electron barrier layer is
Figure BDA0001538184970000052
The evaporation rate of the organic light-emitting layer is
Figure BDA0001538184970000053
The evaporation rate of the hole blocking layer and the electron transport layer is
Figure BDA0001538184970000054
Further, the thickness of the plated film of the hole injection layer is 1-50 nm; the film thickness of the hole transport layer and the electron blocking layer is 10-80 nm; the thickness of the coating film of the organic light-emitting layer is 5-50 nm; the thickness of the coating film of the hole blocking layer and the electron transmission layer is 10-80 nm; the thickness of the Liq layer is 1-5nm, and the thickness of the Al layer is 50-200 nm.
Has the advantages that: the invention provides an oxaspirofluorene triphenylamine derivative, a preparation method and application thereof. The invention takes Ir (MDQ)2(acac) is an organic electroluminescent red phosphorescent device prepared by guest materials, and the maximum brightness efficiency can reach 63.6 lumens per watt. At the same time, efficiencies of 58 lumens per watt can still be achieved with host materials based on the present invention at guest concentrations as low as 0.5 wt%. This efficiency is not only based on the highest efficiency of this guest, but is also achieved at such low guest doping concentrations. In addition, the turn-on voltage of the device can be as low as 2.1V at minimum. Based on the host material of the inventionCompared with the properties of other devices of the same type, the device performance is greatly improved, and important foundations are laid for reducing the cost of organic phosphorescence and realizing commercialization of the organic phosphorescence. According to the invention, an oxygen atom is inserted into spirofluorene triphenylamine to improve rigidity and reduce the singlet state energy of a framework, and meanwhile, the effective molecular weight of the compound is increased by controlling the electron-withdrawing capability of an introduced group and the conjugation degree of the material, so that the singlet state-triplet state difference of the material is greatly reduced. Meanwhile, the material of the invention also shows good resonance energy transfer and stability.
Drawings
Fig. 1 is an ultraviolet-visible absorption spectrum and a fluorescence spectrum of a host material of a host and a guest material prepared in example 1 of the present invention.
FIG. 2 is a transient spectrum of a host material prepared in example 1 of the present invention; (a) transient fluorescence spectra under film and solution (in-line) for OSTFP 2; (b) film and solution (in-line) transient fluorescence spectra for OSTFP 1.
FIG. 3 is a schematic structural diagram of an electroluminescent device of the present invention, in which 1 is a substrate; 2 is a Hole Injection Layer (HIL); 3 is a Hole Transport Layer (HTL); 4 is an Electron Blocking Layer (EBL); 5 is an organic light emitting layer (EML); 6 is a Hole Blocking Layer (HBL); 7 is an Electron Transport Layer (ETL); 8 is an Electron Injection Layer (EIL); and 9 is a cathode.
FIG. 4 is a graph showing the emission spectrum of an electroluminescent device according to the present invention; (a) electroluminescence spectra when subjected to OSTFP1 and OSTFP 2; (b) an electroluminescence spectrogram when CBP is used as a main body and B4PyMPM is used as an electron transmission layer; (c) the electroluminescence spectrum of CBP as main body and TPBI as electron transport layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail 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 embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The method comprises the following steps: 4.23 g of o-bromoiodobenzene is dissolved in 80mL of o-dichlorobenzene under the protection of argon, and 1.83 g of phenoxazine, 0.7 g of cuprous iodide, 0.1 g of 18 crown 6 ether and 5.0 g of potassium carbonate are sequentially added into a 200 mL reaction bottle. After refluxing for 48 hours under argon, the reaction was cooled to room temperature. The solvent was removed by rotary evaporator. The reaction solid was dissolved in 80mL of dichloromethane, and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. Silica gel was added and the resulting solid was spin dried on a column with dichloromethane/petroleum ether 3:7 (vol/vol) to give 3.04 g of 2-bromooxatriphenylamine in 90% yield. Step two: 1.52 g of 2-bromooxatriphenylamine are dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.38mL of n-butyllithium are slowly added to the solution through a constant pressure dropping funnel, and reacted for 1 hour. Then 1.3 g of 2-bromofluorenone were dissolved in 40mL of tetrahydrofuran under argon and added dropwise to the reaction mixture. After 1 hour of the reaction at low temperature, the temperature was gradually raised to room temperature, and after 12 hours of the reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45mL of glacial acetic acid and 10mL of nicotinic acid, refluxed for 4 hours and then cooled to room temperature, then filtered off with suction and rinsed three times with petroleum ether. The solid obtained was chromatographed on a column with dichloromethane/petroleum ether (vol/vol) 4:6 and spin-dried to give 2.1 g of 2-bromooxacyclospirofluorene triphenylamine in 84% yield.
Step three: 2.0 g of 2-bromooxaspirofluorene triphenylamine and 0.4 g of cuprous cyanide were placed in a 100ml two-necked flask with 50ml of azomethylpyrrolidone. After reaction at 180 ℃ for 24 hours, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 water. The organic layer was dried over anhydrous sodium sulfate and spun down to a column of 7:3 dichloromethane/petroleum ether (vol/vol) to give 1.34 g of OSTFP1 in 75% yield.
Example 2
The method comprises the following steps: the same procedure is used in the first step of the embodiment 1.
Step two: the same procedure is used in example 1, step two.
Step three: 2.0 g of 2-bromooxaspirofluorene triphenylamine is dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.0mL of n-butyllithium is slowly added into the solution through a constant pressure dropping funnel and reacted for 1 hour. Then 1.1 g of bis (trimethylphenyl) boron fluoride was dissolved in 40mL of tetrahydrofuran under argon protection and added dropwise to the reaction solution. After 2 hours of reaction at low temperature, gradually warmed to room temperature, and after 12 hours of reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The column was chromatographed with dichloromethane/petroleum ether (7: 3 vol.%) and spin dried to give 1.95 g of OSTFP2 in 73% yield.
Example 3
The method comprises the following steps: the same procedure is used in the first step of the embodiment 1.
Step two: the same procedure is used in example 1, step two.
Step three: 1.52 g of 2-bromooxatriphenylamine are dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.38mL of n-butyllithium are slowly added to the solution through a constant pressure dropping funnel, and reacted for 1 hour. Then 1.3 g of 3-bromofluorenone were dissolved in 40mL of tetrahydrofuran under argon and added dropwise to the reaction mixture. After 1 hour of the reaction at low temperature, the temperature was gradually raised to room temperature, and after 12 hours of the reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45mL of glacial acetic acid and 10mL of nicotinic acid, refluxed for 4 hours and then cooled to room temperature, then filtered off with suction and rinsed three times with petroleum ether. The solid obtained was chromatographed on a column with dichloromethane/petroleum ether (vol/vol) 4:6 and spin-dried to give 1.8 g of 3-bromooxacyclospirofluorene triphenylamine in 72% yield.
Step three: 2.0 g of 3-bromooxaspirofluorene triphenylamine, 0.6 g of 2-azapyridineboronic acid were placed in a 100ml two-necked flask of 60/5ml dioxane/water. After 24 hours at 90 degrees, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 dichloromethane. The organic layer was dried over anhydrous sodium sulfate and spun down to a column of 7:3 dichloromethane/petroleum ether (vol/vol) to give 1.7 g of OSTFP3 in 68% yield.
Example 4
The method comprises the following steps: the same procedure is used in the first step of the embodiment 1.
Step two: the same procedure is used in example 1, step two.
Step three: 1.52 g of 2-bromooxatriphenylamine are dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.38mL of n-butyllithium are slowly added to the solution through a constant pressure dropping funnel, and reacted for 1 hour. Then 1.3 g of 4-bromofluorenone were dissolved in 40mL of tetrahydrofuran under argon and added dropwise to the reaction mixture. After 1 hour of the reaction at low temperature, the temperature was gradually raised to room temperature, and after 12 hours of the reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45mL of glacial acetic acid and 10mL of nicotinic acid, refluxed for 4 hours and then cooled to room temperature, then filtered off with suction and rinsed three times with petroleum ether. The solid obtained was chromatographed on a column with dichloromethane/petroleum ether (vol.4: 6) to give 1.7 g of 4-bromooxacyclospirofluorene triphenylamine in 70% yield.
Step four: 2.0 g of 4-bromooxaspirofluorene triphenylamine, 0.6 g of 2-azapyridineboronic acid were placed in a 100ml two-necked flask of 60/5ml dioxane/water. After 24 hours at 90 degrees, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 dichloromethane. The organic layer was dried over anhydrous sodium sulfate and spun down to a column of 7:3 dichloromethane/petroleum ether (vol/vol) to give 1.6 g of OSTFP4 in 66% yield.
Example 5
The method comprises the following steps: the same procedure is used in the first step of the embodiment 1.
Step two: the same procedure is used in example 1, step two.
Step three: 1.52 g of 2-bromooxatriphenylamine are dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.38mL of n-butyllithium are slowly added to the solution through a constant pressure dropping funnel, and reacted for 1 hour. 1.3 g of 1-bromofluorenone are then dissolved in 40mL of tetrahydrofuran under argon and added dropwise to the reaction mixture. After 1 hour of the reaction at low temperature, the temperature was gradually raised to room temperature, and after 12 hours of the reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45mL of glacial acetic acid and 10mL of nicotinic acid, refluxed for 4 hours and then cooled to room temperature, then filtered off with suction and rinsed three times with petroleum ether. The solid obtained was chromatographed on a column with dichloromethane/petroleum ether (vol/vol) 4:6 and spin-dried to give 1.7 g of 1-bromooxacyclospirofluorene triphenylamine in 70% yield.
Step four: 2.0 g of 1-bromooxaspirofluorene triphenylamine, 1.3 g of 2, 4-diphenyl-1, 3, 5-triazine boronic acid are placed in a 100ml two-necked flask of 60/5ml of dioxane/water. After 24 hours at 90 degrees, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 dichloromethane. The organic layer was dried over anhydrous sodium sulfate and spun down to a column of 7:3 dichloromethane/petroleum ether (vol/vol) to give 2.34 g of OSTFP5 in 73% yield.
Example 6
The method comprises the following steps: the same procedure is used in the first step of the embodiment 1.
Step two: the same procedure is used in example 1, step two.
Step three: 1.52 g of 2-bromooxatriphenylamine are dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.38mL of n-butyllithium are slowly added to the solution through a constant pressure dropping funnel, and reacted for 1 hour. Then 1.84 g of 2, 6-dibromofluorenone are dissolved in 40mL of tetrahydrofuran under the protection of argon and added dropwise to the reaction mixture. After 1 hour of the reaction at low temperature, the temperature was gradually raised to room temperature, and after 12 hours of the reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45mL of glacial acetic acid and 10mL of nicotinic acid, refluxed for 4 hours and then cooled to room temperature, then filtered off with suction and rinsed three times with petroleum ether. The solid obtained was chromatographed on a column with dichloromethane/petroleum ether (vol/vol) 4:6 and spin-dried to give 2.0 g of 2, 6-dibromooxacyclospirofluorene triphenylamine in 69% yield.
Step four: 1.5 g of 2, 6-dibromooxaspirofluorene triphenylamine, 0.4 g of cuprous cyanide were placed in a 100ml two-necked flask with 50ml of azomethylpyrrolidone. After reaction at 180 ℃ for 24 hours, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 water. The organic layer was dried over anhydrous sodium sulfate and dried by spin drying, and the resulting mixture was chromatographed on a column with dichloromethane/petroleum ether (vol/vol) at 7:3 to give 1.2 g of intermediate in 89% yield.
Step five: 1.2 g of the above intermediate, 0.3 g of 2-azapyridineboronic acid, was placed in a 100ml two-necked flask of 60/5ml dioxane/water. After 24 hours at 90 degrees, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 dichloromethane. The organic layer was dried over anhydrous sodium sulfate and spun down to a column of 7:3 dichloromethane/petroleum ether (vol/vol) to give 0.86 g of OSTFP6 in 72% yield.
Example 7
The method comprises the following steps: the same procedure is used in the first step of the embodiment 1.
Step two: the same procedure is used in example 1, step two.
Step three: 1.52 g of 2-bromooxatriphenylamine are dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.38mL of n-butyllithium are slowly added to the solution through a constant pressure dropping funnel, and reacted for 1 hour. Then 1.84 g of 2, 4-dibromofluorenone are dissolved in 40mL of tetrahydrofuran under the protection of argon and added dropwise to the reaction mixture. After 1 hour of the reaction at low temperature, the temperature was gradually raised to room temperature, and after 12 hours of the reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45mL of glacial acetic acid and 10mL of nicotinic acid, refluxed for 4 hours and then cooled to room temperature, then filtered off with suction and rinsed three times with petroleum ether. The solid obtained was chromatographed on a column with dichloromethane/petroleum ether (vol.4: 6) and spin-dried to give 2.2 g of 2, 4-dibromooxacyclospirofluorene triphenylamine, yield 73%.
Step four: 1.5 g of 2, 6-dibromooxaspirofluorene triphenylamine, 0.4 g of cuprous cyanide were placed in a 100ml two-necked flask with 50ml of azomethylpyrrolidone. After reaction at 180 ℃ for 24 hours, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 water. The organic layer was dried over anhydrous sodium sulfate and dried by spin drying, and the resulting mixture was chromatographed on a column with dichloromethane/petroleum ether at 7:3 (vol/vol) to give 1.3 g of intermediate in 90% yield.
Step five: 1.2 g of the above intermediate, 0.3 g of 2-azapyridineboronic acid, was placed in a 100ml two-necked flask of 60/5ml dioxane/water. After 24 hours at 90 degrees, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 dichloromethane. The organic layer was dried over anhydrous sodium sulfate and spun down to a column of 7:3 dichloromethane/petroleum ether (vol/vol) to give 0.90 g of OSTFP7 in 75% yield.
Example 8
The method comprises the following steps: the same procedure is used in the first step of the embodiment 1.
Step two: the same procedure is used in example 1, step two.
Step three: 1.52 g of 2-bromooxatriphenylamine are dissolved in 80mL of tetrahydrofuran under the protection of argon, cooled to-78 ℃, and 2.38mL of n-butyllithium are slowly added to the solution through a constant pressure dropping funnel, and reacted for 1 hour. Then 1.84 g of 3, 7-dibromofluorenone are dissolved in 40mL of tetrahydrofuran under the protection of argon and added dropwise to the reaction mixture. After 1 hour of the reaction at low temperature, the temperature was gradually raised to room temperature, and after 12 hours of the reaction, 5mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80mL of dichloromethane and the organic layer was washed three times with 50mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45mL of glacial acetic acid and 10mL of nicotinic acid, refluxed for 4 hours and then cooled to room temperature, then filtered off with suction and rinsed three times with petroleum ether. The solid obtained was chromatographed on a column with dichloromethane/petroleum ether (vol.: 4: 6) and spin-dried to give 2.2 g of 3, 7-dibromooxacyclospirofluorene triphenylamine, yield 73%.
Step four: 1.5 g of 3, 7-dibromooxaspirofluorene triphenylamine and 0.4 g of cuprous cyanide were placed in a 100ml two-necked flask with 50ml of azomethylpyrrolidone. After reaction at 180 ℃ for 24 hours, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 water. The organic layer was dried over anhydrous sodium sulfate and dried by spin drying, and the resulting mixture was chromatographed on a column with dichloromethane/petroleum ether at 7:3 (vol/vol) to give 1.2 g of intermediate in 88% yield.
Step five: 1.2 g of the above intermediate, 0.3 g of 3-azapyridineboronic acid, was placed in a 100ml two-necked flask of 60/5ml dioxane/water. After 24 hours at 90 degrees, the reaction mixture was gradually cooled to room temperature. The organic layer was separated by extraction with 4X 50 dichloromethane. The organic layer was dried over anhydrous sodium sulfate and spun down to a column of 7:3 dichloromethane/petroleum ether (vol/vol) to give 0.85 g of OSTFP8 in 70% yield.
The following are examples of the use of the compounds of the present invention:
preferred embodiments for the preparation of the device:
as shown in fig. 3, the typical structure of an OLED device is: substrate 1/anode/Hole Injection Layer (HIL) 2/Hole Transport Layer (HTL) 3/Electron Blocking Layer (EBL) 4/organic light emitting layer (EML) 5/Hole Blocking Layer (HBL) 6/Electron Transport Layer (ETL) 7/Electron Injection Layer (EIL) 8/cathode 9.
The substrate is ITO transparent conductive glass substrate, and the hole injection layer is molybdenum trioxide (MoO)3) Or 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN), the hole transport layer may be N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4-N, N ' -dicarbazolylbiphenyl (CBP) or 1,1' -bis-4, 4' -dimethyltriphenylamine cyclohexane (TAPC), the electron transport layer may be 1,3, 5-tris (N-phenyl-2-benzimidazole-2) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen) or 4, 6-bis (3, 5-bis (4-pyridinylphenyl) -2-methylpyrimidine (B4 PyMPM). The device structure can be a single light-emitting layer or a multi-light-emitting layer, and each layer of light-emitting layer can be of a single-doped structure or a multi-doped structure. The red light guest is (acetylacetone) bis (2-methyl dibenzo [ f, h)]Quinoxaline) iridium (Ir (MDQ)2 (acac)). To verify that the guest material of the present invention can work properly at low concentrations, the guest concentration was set at a maximum of 2.0 wt% with a gradient reduction of 1.0 wt% and 0.5 wt%.
Example 9
The compound OSTFP1 of the invention is used as the main material of OLED device, 2.0 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP1:Ir(MDQ)2(acac) (20nm,2.0 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120 nm).
The device preparation process is as follows: the ITO transparent conductive glass substrate is treated by ultrasonic in commercial cleaning agent, washed in deionized water and then is reacted by deionized water, acetone and ethanolAnd (4) cleaning for three times, baking in a clean environment until moisture is completely removed, and treating the ITO conductive glass by using an ultraviolet lamp and ozone. Placing the treated ITO conductive glass in a vacuum chamber, and vacuumizing to 3.0 multiplied by 10-4-4.0×10-4Pa, evaporating HAT-CN as a Hole Injection Layer (HIL) on the ITO conductive glass in vacuum at the evaporation rate of
Figure BDA0001538184970000121
The thickness of the coating film is 10 nm; TAPC is vacuum evaporated on the hole injection layer as a Hole Transport Layer (HTL) and an Electron Blocking Layer (EBL) at a rate of
Figure BDA0001538184970000122
The thickness of the coating film is 45 nm; then adopting a double-source evaporation process, taking the compound OSTFP1 of the invention as a main material, and adopting Ir (MDQ)2(acac) as a first organic light emitting layer (EML) of a dye, controlling an evaporation rate to
Figure BDA0001538184970000123
Coating thickness of 20nm, Ir (MDQ)2The doping concentration of (acac) was 2.0 wt%. Vacuum evaporating a layer of B4PyMPM on the organic light-emitting layer as a Hole Blocking Layer (HBL) and an Electron Transport Layer (ETL) of the device at an evaporation rate of
Figure BDA0001538184970000124
The thickness of the coating film is 45 nm; and vacuum evaporating Liq and an Al layer on the electron transport layer to be used as a cathode of the device, wherein the thickness of the Liq layer is 2nm, and the thickness of the Al layer is 120 nm.
Example 10
The compound OSTFP1 of the invention is used as the main material of OLED device, 1.0 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP1:Ir(MDQ)2(acac) (20nm,1.0 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 11
Using the compound OSTFP1 of the present inventionAs OLED device host material, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP1:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 12
The compound OSTFP2 of the invention is used as the main material of OLED device, 2.0 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP2:Ir(MDQ)2(acac) (20nm,2.0 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 13
The compound OSTFP2 of the invention is used as the main material of OLED device, 1.0 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP2:Ir(MDQ)2(acac) (20nm,1.0 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 14
The compound OSTFP2 of the invention is used as the main material of OLED device, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP2:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 15
The compound OSTFP3 of the invention is used as the main material of OLED device, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP3:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 16
The compound OSTFP4 of the invention is used as the main material of OLED device, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP4:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 17
The compound OSTFP5 of the invention is used as the main material of OLED device, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP5:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 18
The compound OSTFP6 of the invention is used as the main material of OLED device, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP6:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 19
The compound OSTFP7 of the invention is used as the main material of OLED device, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP7:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120nm), and device fabrication was the same as in example 9.
Example 20
The compound OSTFP8 of the invention is used as the main material of OLED device, 0.5 wt% Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is:
ITO/HAT-CN(10nm)/TAPC(40nm)TCTA(10nm)/OSTFP8:Ir(MDQ)2(acac) (20nm,0.5 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120 n)m), device fabrication procedure same as example 9.
Comparative example 1
4,4' -bis (9-Carbazole) Biphenyl (CBP) is adopted as the main material of the OLED device, Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is: ITO/HAT-CN (10nm)/TAPC (40nm) TCTA (10nm)/CBP Ir (MDQ)2(acac)(20nm,
2.0 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120 nm).
The device preparation process is as follows: the ITO transparent conductive glass substrate is subjected to ultrasonic treatment in a commercial cleaning agent, washed in deionized water, repeatedly washed three times by using the deionized water, acetone and ethanol, baked in a clean environment until moisture is completely removed, and treated by an ultraviolet lamp and ozone. Placing the treated ITO conductive glass in a vacuum chamber, and vacuumizing to 3.0 multiplied by 10-4～4.0×10-4Pa, evaporating HAT-CN as a Hole Injection Layer (HIL) on the ITO conductive glass in vacuum at the evaporation rate of
Figure BDA0001538184970000151
The thickness of the coating film is 10 nm; TAPC is vacuum evaporated on the hole injection layer as a Hole Transport Layer (HTL) and an Electron Blocking Layer (EBL) at a rate of
Figure BDA0001538184970000152
The thickness of the coating film is 45 nm; then, a double-source evaporation process is adopted, CBP is used as a main material, Ir (MDQ) is adopted2(acac) organic light-emitting layer (EML) as a dye, the evaporation rate being controlled to
Figure BDA0001538184970000153
Coating thickness of 20nm, Ir (MDQ)2The doping concentration of (acac) was 2.0 wt%; vacuum evaporating a layer of B4PyMPM on the organic light-emitting layer as a Hole Blocking Layer (HBL) and an Electron Transport Layer (ETL) of the device at an evaporation rate of
Figure BDA0001538184970000154
The thickness of the coating film is 45 nm; vacuum evaporating Liq and Al layers on the electron transport layer as a cathode of the device, wherein the Liq layerThe thickness is 2nm, and the thickness of the Al layer is 120 nm.
Comparative example 2
4,4' -bis (9-Carbazole) Biphenyl (CBP) is adopted as the main material of the OLED device, Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is: ITO/HAT-CN (10nm)/TAPC (40nm) TCTA (10nm)/CBP Ir (MDQ)2(acac)(20nm,
2.0 wt% doping concentration)/TPBI (45nm)/Liq (2nm)/Al (120 nm).
The device preparation process is as follows: the ITO transparent conductive glass substrate is subjected to ultrasonic treatment in a commercial cleaning agent, washed in deionized water, repeatedly washed three times by using the deionized water, acetone and ethanol, baked in a clean environment until moisture is completely removed, and treated by an ultraviolet lamp and ozone. Placing the treated ITO conductive glass in a vacuum chamber, and vacuumizing to 3.0 multiplied by 10-4～4.0×10-4Pa, evaporating HAT-CN as a Hole Injection Layer (HIL) on the ITO conductive glass in vacuum at the evaporation rate of
Figure BDA0001538184970000162
The thickness of the coating film is 10 nm; TAPC is vacuum evaporated on the hole injection layer as a Hole Transport Layer (HTL) and an Electron Blocking Layer (EBL) at a rate of
Figure BDA0001538184970000163
The thickness of the coating film is 45 nm; then, a double-source evaporation process is adopted, CBP is used as a main material, Ir (MDQ) is adopted2(acac) organic light-emitting layer (EML) as a dye, the evaporation rate being controlled to
Figure BDA0001538184970000164
Coating thickness of 20nm, Ir (MDQ)2The doping concentration of (acac) was 2.0 wt%; vacuum evaporating a TPBI layer as a Hole Blocking Layer (HBL) and an Electron Transport Layer (ETL) of the device on the organic light-emitting layer at a rate of
Figure BDA0001538184970000165
The thickness of the coating film is 45 nm; vacuum evaporating Liq and Al layers on the electron transport layer to be used as a cathode of the device, wherein the Liq layer is thickThe degree is 2nm, and the thickness of the Al layer is 120 nm.
Comparative example 3
Adopts oxaspirofluorene triphenylamine (OSTFP) as the main material of OLED device, Ir (MDQ)2(acac) is a red phosphorescent dye, and the device structure is: ITO/HAT-CN (10nm)/TAPC (40nm) TCTA (10nm)/OSTFP Ir (MDQ)2(acac)(20nm,
2.0 wt% doping concentration)/B4 PyMPM (45nm)/Liq (2nm)/Al (120 nm).
The device fabrication procedure was the same as in example 9.
The device structures of examples 9-20 and comparative examples 1-3 are shown in Table 1:
TABLE 1
Figure BDA0001538184970000161
Figure BDA0001538184970000171
The current-luminance-voltage characteristics of the device were obtained with a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, and the electroluminescence spectra were measured with a Photo research PR655 spectrometer, all measurements being carried out in a room temperature atmosphere.
The device data for examples 9-20 and comparative examples 1-3 are shown in Table 2:
TABLE 2
Figure BDA0001538184970000181
From the above-mentioned effects of the devices 9-20, the host material of the present invention can be applied to an organic electroluminescent red phosphorescent device, and can obtain high-efficiency electroluminescent performance. When the material of the invention is used as the host material (example 11), it is based on Ir (MDQ)2(the organic electroluminescent red phosphorescent device of acac, maximum luminance efficiency of 63.6 lumens per watt. at guest concentrations as low as 0.5 wt.% (example 12), based on the inventionThe body material of (a) still achieves an efficiency of 58 lumens per watt. This efficiency is not only based on the highest efficiency of this guest, but is also achieved at such low guest doping concentrations. Whereas for the comparative example 1 device, at this concentration, a peak of the exciplex was generated (fig. 4 b). Even when the concentration was increased to 2.0 wt%, a peak of the exciplex thereof was observed. Therefore, we transpose the B4PyMPM transport layer to TPBI to avoid such effects. From the device effect, even at a guest concentration of 2.0 wt%, the resonance energy transfer of the conventional host material is still significantly insufficient (fig. 4c), and the efficiency is much lower than that of the host material of the present invention. In addition, the turn-on voltage of the device can be as low as 2.1V at minimum. Unsubstituted oxaspirofluorene triphenylamine (OSTFP) is used as the main material of the OLED device (comparative example 3), and the performance of the prepared device is still far lower than that of the devices prepared in examples 9-20. Compared with the properties of other devices of the same type, the device performance based on the host material of the invention is greatly improved, and an important foundation is laid for reducing the cost of organic phosphorescence and realizing the commercialization of the organic phosphorescence in the future.
Meanwhile, compared with the published Chinese patent CN104892578A fluorine spiro triphenylamine derivative and the application thereof, the main body material of the invention has smaller singlet state-triplet state energy level. By inserting oxygen atoms into the triphenylamine, on one hand, the rigidity of the material can be improved, and on the other hand, the electron donating capability of the triphenylamine part can be enhanced, so that the difference between the singlet state energy level and the singlet state-triplet state energy level is reduced. The latter presents more evident advantages from the technical results. Compared with blue bis (4, 6-difluorophenylpyridine-N, C2') picolinoylated iridium (FIrpic) in the reference fluorenylspirotriphenylamine derivative and its use (CN104892578A), ir (mdq)2(acac) having red light emission is used in the present invention. At the same time, the highest power efficiency achieved by the reference even at high doping concentrations (15 wt%) is only 36 lumens per watt, much lower than the 58 lumens per watt achieved by the present invention even at very low concentrations (0.5 wt%). At the same time, the present document aims to solve the problem of obtaining high efficiency at low concentrations, while the reference document makes no mention. Based on the different contents of the problem and the outstanding technical result of the invention, the file of the invention has better advantages compared with the comparison file.
In conclusion, the spirofluorene triphenylamine is inserted with an oxygen atom to improve rigidity and reduce the singlet state energy of a framework, and meanwhile, the electron-withdrawing capability of an introduced group and the conjugation degree of a material are controlled to increase the effective molecular weight of the compound, so that the singlet state-triplet state difference of the material is greatly reduced. Meanwhile, the material of the invention also shows good resonance energy transfer and stability.
The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. The application of the oxaspirofluorene triphenylamine derivative in preparing an organic electroluminescent red phosphorescent device is characterized in that the oxaspirofluorene triphenylamine derivative has a chemical structure shown in a formula (I):
Figure DEST_PATH_IMAGE001
（Ⅰ）；
wherein the main body is oxaspirofluorene triphenylamine, and the substituents R1-R8 are respectively and independently selected from hydrogen, cyano, bis (trimethylphenyl) boron fluoride, 2-azapyridine, 3-azapyridine or 2, 4-diphenyl-1, 3, 5-triazine.
2. Use according to claim 1, characterized in that said oxaspirofluorene triphenylamine derivative comprises a derivative of the following formulae ii to ix:
Figure 272366DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE003
（Ⅶ） （Ⅷ） （Ⅸ）。
3. organic red phosphorescent device of electricity generation, including glass, the conductive glass substrate layer of attaching to on glass, the hole injection layer with the laminating of conductive glass substrate layer, the hole transport layer with the laminating of hole injection layer, the luminescent layer with the laminating of hole transport layer, the hole barrier layer with the laminating of luminescent layer, the electron transport layer with the laminating of hole barrier layer, the cathode layer with the laminating of electron transport layer, its characterized in that: the light-emitting layer is composed of a host material and a guest material, the host material is the oxaspirofluorene triphenylamine derivative of claim 1 or 2, and the guest material is a red light iridium complex with a ring metal ligand.
4. The organic electroluminescent red phosphorescent device according to claim 3, wherein: the red-light iridium complex is red-light acetylacetone bis (2-methyl dibenzo [ F, H ] quinoxaline) iridium.
5. The organic electroluminescent red phosphorescent device according to claim 3, wherein: the doping concentration of the guest material is not higher than 2.0 wt%.
6. A method of preparing an organic electroluminescent red phosphorescent device according to any one of claims 3, 4 or 5, comprising the steps of: (1) pretreating an ITO transparent conductive glass substrate; (2) vacuum evaporating a hole injection layer on the ITO conductive glass; (3) vacuum evaporating a hole transport layer and an electron blocking layer on the hole injection layer; (4) adopting a double-source evaporation process, taking the oxaspirofluorene triphenylamine derivative as a host material and the red light iridium complex with a ring metal ligand as an organic light-emitting layer of a guest material, and carrying out vacuum evaporation on a hole blocking layer and an electron transport layer on the organic light-emitting layer; (5) and vacuum evaporating a cathode layer on the electron transport layer.
7. The method of claim 6, wherein the hole injection layer is molybdenum trioxide or 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene, and the hole transport layer is N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 4-N, N ' -dicarbazolylbiphenyl or 1,1' -bis-4, 4' -dimethyltriphenylamine cyclohexane; the electron transport layer is 1,3, 5-tri (N-phenyl-2-benzimidazole-2) benzene, 4, 7-diphenyl-1, 10-phenanthroline or 4, 6-bis (3, 5-di (4-pyridine) phenyl) -2-methylpyrimidine; the cathode layer is Liq and Al.
8. The method of claim 6, wherein the hole injection layer is evaporated at a rate of 0.1 to 0.5 a/s; the evaporation rate of the hole transport layer and the electron blocking layer is 1-10A/s; the evaporation rate of the organic light-emitting layer is 1-10A/s; the evaporation rate of the hole blocking layer and the electron transport layer is 1-10A/s.
9. The method of claim 6, wherein the hole injection layer has a plating film thickness of 1-50 nm; the film thickness of the hole transport layer and the electron blocking layer is 10-80 nm; the thickness of the coating film of the organic light-emitting layer is 5-50 nm; the thickness of the coating film of the hole blocking layer and the electron transmission layer is 10-80 nm; the thickness of the Liq layer is 1-5nm, and the thickness of the Al layer is 50-200 nm.
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