CN106632480A - n-type thermal excitation delayed fluorescence aromatic phosphine oxide main body materials based on dibenzofuran groups as well as synthetic method and application thereof - Google Patents

n-type thermal excitation delayed fluorescence aromatic phosphine oxide main body materials based on dibenzofuran groups as well as synthetic method and application thereof Download PDF

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CN106632480A
CN106632480A CN201710068312.XA CN201710068312A CN106632480A CN 106632480 A CN106632480 A CN 106632480A CN 201710068312 A CN201710068312 A CN 201710068312A CN 106632480 A CN106632480 A CN 106632480A
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thermal excitation
dibenzofurans
delayed fluorescence
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excitation delayed
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CN106632480B (en
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许辉
张静
韩春苗
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Heilongjiang University
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    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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Abstract

The invention discloses n-type thermal excitation delayed fluorescence aromatic phosphine oxide main body materials based on dibenzofuran groups as well as a synthetic method and application thereof, and relates to phosphine oxide main body materials as well as a synthetic method and application thereof. The invention aims to solve the technical problem that the stability of an excited state of a thermal excitation delayed fluorescence molecule is poor due to the fact that photooxidation and electrooxidation processes of a thermal excitation delayed fluorescent material are easily generated in the operation process of a device. The material is formed by introducing 2 to 4 diphenyl phosphine oxide groups at 2, 4, 6, 8 positions of dibenzofuran. The method comprises the following steps: mixing raw materials, pouring the mixed materials into ice water, and extracting to obtain an organic layer; oxidizing, extracting, drying and purifying to obtain a finished product. According to the main body material disclosed by the invention, the excited state of the thermal excitation delayed fluorescent molecule is stabilized by the electron withdrawing induction capability of the dibenzofuran aromatic phosphine oxide main body materials, thereby obtaining high-efficiency stable thermal excitation delayed fluorescence emission. The material serving as a main body of a luminous layer or an exciton block layer, disclosed by the invention, is used for preparing an electroluminescent device.

Description

Based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen main body material Material, synthetic method and its application
Technical field
The present invention relates to a class n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part, synthetic method and its application.
Background technology
High efficiency, the organic electroluminescent of low-voltage driving bring revolutionary innovation for the development of light emitting diode.Have The research of machine luminescent material and device causes extensive concern and the further investigation of people.Organic electroluminescent LED is referred to as Third generation plane shows and lighting engineering there is prominent advantage at aspects such as energy-conserving and environment-protective, and organic semiconducting materials are divided into p-type And N-shaped, most of organic semiconducting materials are p-types, it means that most of materials can only pass positive charge.At present, N-shaped is organic The development of semiconductor lags far behind p-type organic semiconducting materials, and with high electron mobility, thermodynamically stable N-shaped has Machine semiconductor is extremely short.It is general at present in order to effectively using the singlet state and triplet exciton produced during electroluminescent All over by the way of usinging being that electroluminescent phosphorescence is built using phosphorescent coloring, but the heavy metal involved by phosphorescent coloring not only costliness and And environment is polluted, in the urgent need to being substituted using other materials.Fluorescence organic functional material has been considered as organic light emission For it contains the more preferable potential substitute of the phosphor material of rare metal or noble metal in diode (OLED), because more may be used Inexpensive and high performance device can be realized.In the recent period, it is referred to as the thermal excitation delayed fluorescence of third generation organic electroluminescent technology Technology makes great progress, and wherein thermal excitation delayed fluorescence dyestuff can pass through itself triplet state to the reversion gap of singlet Between alter jump and make triplet excitons be converted into singlet exciton, it is and then luminous using it, so as to theoretically realize 100% interior amount Sub- efficiency.And thermal excitation delayed fluorescence dyestuff is pure organic compound.But, currently for the master of thermal excitation delayed fluorescence dyestuff The research of body material is also very limited, particularly, more limited for the research of n-type thermal excitation delayed fluorescence material.Therefore, Need for being adapted to their material of main part come autotelic exploitation the characteristics of thermal excitation delayed fluorescence dyestuff.
Research shows, efficiently remains and be difficult to what is obtained with stable Blue OLED.Thermal excitation delayed fluorescence material is in device Photooxidation and electro-oxidation process are susceptible in part running, high-energy is effectively decomposed in the wherein combination of electroxidation and photooxidation Triplet, therefore, it can suppress such degradation process by MOLECULE DESIGN and device optimization, introduce one pole with stronger The material for leading electronic capability is conducive to stablizing thermal excitation delayed fluorescence molecule, improves device efficiency.
The content of the invention
The present invention is to solve thermal excitation delayed fluorescence material is susceptible to photooxidation and electric oxygen in device running Change process, causes the technical problem of thermal excitation delayed fluorescence molecular-excited state stability difference, there is provided one kind is based on dibenzo furan Mutter group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part, synthetic method and its application.
Based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part, the material is by hexichol And 2～4 diphenylphosphine oxygen groups compositions are introduced on 2,4,6,8 positions of furans, molecular structural formula is as follows：
Wherein X is H or Ph2OP, Y are H or Ph2OP, Z are H or Ph2OP, and Y is H when different with Z；
When X, Y are H, Z is Ph2During OP, compound is 2,4DBFDPO, and its structural formula is：
When Y is Ph2OP, when X, Z are H, compound is 2,8DBFDPO, and its structural formula is：
When Y and Z is Ph2When OP, X are H, compound is 2,4,8DBFTPO, and its structural formula is：
When X, Y are Ph2When OP, Z are hydrogen, compound is 2,4,6DBFTPO, and its structural formula is：
When X, Y, Z are Ph2During OP, compound is 2,4,6,8DBFQPO, and its structural formula is：
Based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part synthetic method, its feature exists It is as follows in the synthetic method：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 1～6mmol, 1～6mmol anhydrous second The DMF mixing of sour sodium, 0.001～0.01mmol palladiums and 5～10ml, reacts 10～36 hours, in pouring frozen water into, extraction, Organic layer is obtained, organic layer adds 1ml H after being dried2O2Oxidation, then Jing after extraction, being dried, with the mixing of ethanol and ethyl acetate Solvent is eluent column chromatography purifying, obtains based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen main body material Material (many phosphine oxygen dibenzofuran group phosphine oxygen).
Described diphenylphosphine is (1～2) ﹕ 1, palladium with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material It is (0.001～0.002) ﹕ 1, anhydrous sodium acetate and bromo hexichol with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material The amount ratio of base phosphine epoxide dibenzofurans material is (1～2) ﹕ 1.
Ethanol and the volume ratio of ethyl acetate are 1 ﹕ 20 in the mixed solvent of the ethanol and ethyl acetate.
Master of the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material based on dibenzofurans group as luminescent layer Body material exciton barrier-layer is used to prepare electroluminescent device.
The material of main part of the present invention can effectively suppress thermal excitation delayed fluorescence material to occur in device running Photooxidation and electro-oxidation process, the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen based on dibenzofurans group prepared by the present invention Material of main part can realize the efficient thermal excitation delayed fluorescence blue-light device that ultralow pressure drives, and its current efficiency reaches maximum 24.24cd·A-1, power efficiency reach maximum 19.56lmW. the present invention provide the n-type based on dibenzofurans group Thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part is based on 2- diphenylphosphine epoxide dibenzofurans, phosphine oxygen (P=O) group Aromatic group is coupled together by C-P saturated bonds, conjugation can be effectively blocked, make parent itself that there is higher triplet state Energy level, while P=O groups have the effect of polar molecule, can put forward high molecular electron injection transmittability.And with certain Electron injection and transmittability.The modification that the present invention is carried out by many phosphine oxygen groups, by adjusting the number of modification group and repairing Adorn position to regulate and control the carrier transport ability of whole molecule.So as in high triplet excitation state energy level and good carrier Balance is tried to achieve between injection transmittability.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of the present invention based on dibenzofurans group is used for electroluminescent Luminescent device includes advantages below：
1st, higher triplet is kept, it is ensured that effective transmission of the energy from main body to object.
2nd, carrier injection and the transmittability of electroluminescent device material are improved, with the n- based on dibenzofurans group Blue light electroluminescence device is opened bright voltage drop by blue light electroluminescence device prepared by type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part It is low to 2.8V, with good thermodynamic stability, cracking temperature is 407 DEG C -488 DEG C, while improve organic electroluminescent The luminous efficiency of material and brightness, present invention is mainly applied in organic electroluminescent diode apparatus.
The present invention both can be made based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group For the luminescent layer material of main part of luminescent device, it is also possible to as the exciton blocking layer material of luminescent device.
Description of the drawings
Fig. 1 is to test a purple based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Outer fluorescence spectrum spectrogram and the fluorescence spectra being dissolved in dichloromethane solvent and phosphorescence spectrum figure, ■ is represented based on dibenzo furan Mutter the ultraviolet spectrogram of the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part in dichloromethane solvent of group, is represented It is dissolved in based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group glimmering in dichloromethane solvent Light spectrogram, ● represent based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part phosphorescence spectrum of dibenzofurans group Figure；
Fig. 2 is to test the heat based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Weight analysis figure；
Fig. 3 is to test two purples based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofuran group group Outer fluorescence spectrum spectrogram and the fluorescence spectra being dissolved in dichloromethane solvent and phosphorescence spectrum figure, ■ is represented based on dibenzo furan The ultraviolet spectrogram muttered in the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part dichloromethane solvent of group, represents base It is dissolved in dichloromethane solvent in the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group Fluorescence spectra, ● represent based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part phosphorescence light of dibenzofurans group Spectrogram；
Fig. 4 is to test two heat based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofuran group group Weight analysis spectrogram；
Fig. 5 is to test the three n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts for being based on dibenzofurans group Ultraluminescence spectrum spectrogram and the fluorescence spectra that is dissolved in dichloromethane solvent and phosphorescence spectrum figure, ■ represented based on hexichol And the ultraviolet spectrogram in the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part dichloromethane solvent of furan group, tables Show and be dissolved in dichloromethane solvent based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Fluorescence spectra, ● represent based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part phosphorescence light of dibenzofurans group Spectrogram；
Fig. 6 is to test three heat based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Weight analysis spectrogram；
Fig. 7 is to test four purples based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Outer fluorescence spectrum spectrogram and the fluorescence spectra being dissolved in dichloromethane solvent and phosphorescence spectrum figure, ■ is represented based on dibenzo furan The ultraviolet spectrogram muttered in the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part dichloromethane solvent of group, represents base The fluorescence being dissolved in the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group in dichloromethane solvent Spectrogram, ● represent based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part phosphorescence spectrum of dibenzofurans group Figure；
Fig. 8 is to test four heat based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Weight analysis spectrogram；
Fig. 9 is to test five purples based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Outer fluorescence spectrum spectrogram and the fluorescence spectra being dissolved in dichloromethane solvent and phosphorescence spectrum figure, ■ is represented based on dibenzo furan The ultraviolet spectrogram muttered in the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part dichloromethane solvent of group, represents base The fluorescence being dissolved in the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group in dichloromethane solvent Spectrogram, ● represent based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part phosphorescence spectrum of dibenzofurans group Figure；
Figure 10 is to test the five n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group Thermogravimetric analysis spectrogram；
Figure 11 is to test a n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group The voltage-current density relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 12 is to test a n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group The voltage-brightness relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 13 is to test a n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group The luminance-current efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 14 is to test a n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group Brightness-the power efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 15 is to test a n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group The current density of electroluminescent dark blue smooth phosphorescent devices-external quantum efficiency relation curve efficiency；
Figure 16 is to test a bipolar thermal excitation delayed fluorescence aromatic phosphines oxygen main body material of n-type based on dibenzofurans group The electroluminescent light spectrogram of the electroluminescent dark blue smooth phosphorescent devices of material；
Figure 17 is to test the two n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofuran group group The voltage-current density relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 18 is to test the two n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofuran group group The voltage-brightness relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 19 is to test the two n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofuran group group The luminance-current efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 20 is to test the two n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofuran group group Brightness-the power efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 21 is to test the two n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofuran group group The current density of electroluminescent dark blue smooth phosphorescent devices-external quantum efficiency relation curve efficiency；
Figure 22 is to test the two n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofuran group group The electroluminescent light spectrogram of electroluminescent dark blue smooth phosphorescent devices；
Figure 23 is to test the three n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The voltage-current density relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 24 is to test the three n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The voltage-brightness relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 25 is to test the three n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The luminance-current efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 26 is to test the three n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group Brightness-the power efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 27 is to test the three n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The current density of electroluminescent dark blue smooth phosphorescent devices-external quantum efficiency relation curve efficiency；
Figure 28 is to test the three n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The electroluminescent light spectrogram of electroluminescent dark blue smooth phosphorescent devices；
Figure 29 is to test the four n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The voltage-current density relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 30 is to test the four n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The voltage-brightness relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 31 is to test the four n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The luminance-current efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 32 is to test the four n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group Brightness-the power efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 33 is to test the four n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The current density of electroluminescent dark blue smooth phosphorescent devices-external quantum efficiency relation curve efficiency；
Figure 34 is to test the four n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The electroluminescent light spectrogram of electroluminescent dark blue smooth phosphorescent devices；
Figure 35 is to test the five n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The voltage-current density relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 36 is to test the five n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The voltage-brightness relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 37 is to test the five n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The luminance-current efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 38 is to test the five n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group Brightness-the power efficiency relation curve of electroluminescent dark blue smooth phosphorescent devices；
Figure 39 is to test the five n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The current density of electroluminescent dark blue smooth phosphorescent devices-external quantum efficiency relation curve efficiency；
Figure 40 is to test the five n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main parts based on dibenzofurans group The electroluminescent light spectrogram of electroluminescent dark blue smooth phosphorescent devices.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, also including between each specific embodiment Any combination.
Specific embodiment one：Present embodiment is based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen Material of main part, the material is constituted by introducing 2～4 diphenylphosphine oxygen groups on 2,4,6,8 positions of dibenzofurans, point Subformula is as follows：
Wherein X is H or Ph2OP, Y are H or Ph2OP, Z are H or Ph2OP, and Y is H when different with Z；
When X, Y are H, Z is Ph2During OP, compound is 2,4DBFDPO, and its structural formula is：
When Y is Ph2OP, when X, Z are H, compound is 2,8DBFDPO, and its structural formula is：
When Y and Z is Ph2When OP, X are H, compound is 2,4,8DBFTPO, and its structural formula is：
When X, Y are Ph2When OP, Z are hydrogen, compound is 2,4,6DBFTPO, and its structural formula is：
When X, Y, Z are Ph2During OP, compound is 2,4,6,8DBFQPO, and its structural formula is：
Specific embodiment two：Dibenzofurans group n-type thermal excitation delayed fluorescence is based on described in specific embodiment one Aromatic phosphines oxygen material of main part synthetic method, it is characterised in that the synthetic method is as follows：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 1～6mmol, 1～6mmol anhydrous second The DMF mixing of sour sodium, 0.001～0.01mmol palladiums and 5～10ml, reacts 10～36 hours, in pouring frozen water into, extraction, Organic layer is obtained, organic layer adds 1ml H after being dried2O2Oxidation, then Jing after extraction, being dried, with the mixing of ethanol and ethyl acetate Solvent is eluent column chromatography purifying, obtains based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen main body material Material.
Specific embodiment three：Present embodiment and diphenylphosphine and bromo described unlike specific embodiment two The amount ratio of diphenylphosphine epoxide dibenzofurans material is (1～2) ﹕ 1, palladium and bromodiphenyl-phosphine epoxide dibenzofurans The amount ratio of material is (the amount ratio of 0.001～0.002) ﹕ 1, anhydrous sodium acetate and bromodiphenyl-phosphine epoxide dibenzofurans material For (1～2) ﹕ 1.Other are identical with specific embodiment two.
Specific embodiment four：Present embodiment and the ethanol unlike specific embodiment two and ethyl acetate Ethanol and the volume ratio of ethyl acetate are 1 ﹕ 20 in mixed solvent.Other are identical with specific embodiment two.
Specific embodiment five：Present embodiment from unlike specific embodiment two by 1mmol bromodiphenyl-phosphines The DMF of epoxide dibenzofurans, the diphenylphosphine of 4mmol, the anhydrous sodium acetate of 4mmol, 0.006mmol palladiums and 6ml is mixed Close.Other are identical with specific embodiment two.
Specific embodiment six：Present embodiment from unlike specific embodiment two by 1mmol bromodiphenyl-phosphines The DMF mixing of epoxide phenylate, the diphenylphosphine of 4mmol, the anhydrous sodium acetate of 4mmol, 0.007mmol palladiums and 7ml.Other It is identical with specific embodiment two.
Specific embodiment seven：Present embodiment from unlike specific embodiment two by 1mmol bromodiphenyl-phosphines The DMF of epoxide dibenzofurans, the diphenylphosphine of 5mmol, the anhydrous sodium acetate of 5mmol, 0.009mmol palladiums and 8ml is mixed Close.Other are identical with specific embodiment two.
Specific embodiment eight：Present embodiment from unlike specific embodiment two by 1mmol bromodiphenyl-phosphines The DMF of epoxide dibenzofurans, the diphenylphosphine of 5mmol, the anhydrous sodium acetate of 5mmol, 0.008mmol palladiums and 9ml is mixed Close.Other are identical with specific embodiment two.
Specific embodiment nine：Present embodiment from unlike specific embodiment two by 1mmol bromodiphenyl-phosphines The DMF of epoxide dibenzofurans, the diphenylphosphine of 5mmol, the anhydrous sodium acetate of 5mmol, 0.01mmol palladiums and 10ml is mixed Close.Other are identical with specific embodiment two.
Specific embodiment ten：Dibenzofurans group n-type thermal excitation delayed fluorescence is based on described in specific embodiment one The application of aromatic phosphines oxygen material of main part, the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material based on dibenzofurans group It is used to prepare electroluminescent device as the material of main part exciton barrier-layer of luminescent layer.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen main body material described in present embodiment based on dibenzofurans group Expect as follows for the method for preparing electro phosphorescent device as luminescent layer：
First, the glass or plastic supporting base for cleaning Jing deionized waters is put into vacuum evaporation instrument, and vacuum is 1 × 10-6Mbar, Evaporation rate is set to 0.1～0.3nm s-1, on glass or plastic supporting base deposition material be tin indium oxide (ITO), thickness be 1～ The anode conductive layer of 100nm；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 2～10nm hole injection layers；
3rd, hole transport layer material NPB is deposited with hole injection layer, thickness is obtained for 20～40nm hole transmission layers；
4th, barrier material mCP is deposited with hole transmission layer, thickness is obtained for 5～15nm exciton barrier-layers；
5th, n-type thermal excitation delayed fluorescence of the emitting layer material based on dibenzofurans group is deposited with exciton barrier-layer The mixture of aromatic phosphines oxygen material of main part and DMAC (dimethyl acetamide), thickness is 5～50nm luminescent layers；
6th, continue to be deposited with n-type thermal excitation delayed fluorescence of the hole blocking layer based on dibenzofurans group on luminescent layer Aromatic phosphines oxygen material of main part, thickness is 5～40nm hole blocking layers；
7th, electron transport layer materials Bphen is deposited with hole blocking layer, thickness is 10～80nm electron transfer layers；
8th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 1～10nm electron injecting layers；
9th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 1～100nm, obtains electro phosphorescent Optical device.
Metal described in step 8 is calcium, magnesium, silver, aluminium, calcium alloy, magnesium alloy, silver alloy or aluminium alloy.
Using following experimental verifications effect of the present invention：
Experiment one：This experiment is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Synthetic method follow these steps to realize：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 1mmol, 1mmol anhydrous sodium acetate, The palladium of 0.001mmol and the DMF mixing of 10ml, reaction is poured into frozen water after 10 hours, and organic layer, organic layer is obtained by extraction 1ml H are added after drying2O2Oxidation, then Jing extraction, after being dried with the volume ratio of ethanol and ethyl acetate as 1:20 is eluent post Chromatographic purifying, obtains 2,4- diphenylphosphine epoxide dibenzofurans.
The amount ratio of diphenylphosphine and bromodiphenyl-phosphine epoxide dibenzofurans material wherein described in this experimental procedure two For 1 ︰ 1, anhydrous sodium acetate is 1 ︰ 1, palladium and bromo hexichol with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material The amount ratio of base phosphine epoxide dibenzofurans material is 0.001 ︰ 1；
The bromodiphenyl-phosphine epoxide dibenzofurans that this experiment is obtained is 2,4, diphenylphosphine epoxide dibenzofurans, knot Structure formula is
It is 2 that this experiment obtains the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group, 4DBFDPO。
The 2,4DBFDPO of multifunction modification prepared by this test are detected using NMR, testing result is as follows：
1H NMR(TMS,CDCl3,400MHz):=8.174 (d, J=7.6Hz, 2H), 7.819-7.765 (qd, J1= 1.2Hz,J2=7.6Hz, J3=13.2Hz, 2H), 7.655-7.603 (td, J1=1.2Hz, J2=7.2Hz, 8H), 7.478- 7.430(td,J1=1.2Hz, J2=7.2Hz, 6H), 7.361-7.314ppm (td, J1=3.2Hz, J2=8Hz, 8H)；LDI- TOF:M/z (%):584(100)[M+]；Elemental analysis (%) for C36H26O2P2S:H,4.48；O,5.47；S, 5.48；
The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2 based on dibenzofurans group that this experiment is obtained, The Ultraluminescence spectrum of 4DBFDPO, phosphorescence spectrum spectrogram is as shown in Figure 1.
The n-type thermal excitation delayed fluorescence based on dibenzofurans group that this experiment is obtained is based on aromatic phosphines oxygen main body material The thermogravimetric analysis spectrogram of 2,4DBFDPO of material is as shown in Fig. 2 dibenzofuran group phosphine oxygen material of main part 2,4DBFDPO as seen from the figure Cracking temperature be 407 DEG C.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group is (and empty as luminescent layer Cave barrier layer) it is as follows for preparing the method for electro phosphorescent device：
First, the plastic supporting base that Jing deionized waters are cleaned is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is that the anode of 1 0nm is led Electric layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material NPB is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, barrier material mCP is deposited with hole transmission layer, thickness is obtained for 15nm exciton barrier-layers；
5th, n-type thermal excitation delayed fluorescence of the emitting layer material based on dibenzofurans group is deposited with exciton barrier-layer The mixture of aromatic phosphines oxygen material of main part and DMAC (dimethyl acetamide), thickness is 50nm luminescent layers；
6th, continue to be deposited with based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of dibenzofurans group on luminescent layer Material forms hole blocking layer, and thickness is 40nm hole blocking layers；
7th, electron transport layer materials Bphen is deposited with hole blocking layer, thickness is 80nm electron transfer layers；
8th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
9th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device Part.
Metal described in step 8 is aluminium.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part in this experiment based on dibenzofurans group is both electricity The luminescent layer material of main part of phosphorescent device, is again the hole barrier layer material of electro phosphorescent device.
The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/NPB(40nm)/mCP(15nm)/2, 4DBFDPO:DMAC (20%) 50nm/2,4DBFDPO (40nm)/Bphen (80nm)/LiF (10nm)/Al.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 11, thus figure understands to be based on the voltage-current density relation curve of blue light electroluminescence phosphorescent devices prepared by 4DBFDPO The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4DBFDPO materials of dibenzofurans group have semiconductor special Property, its threshold voltage is 3.5V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 12, thus figure understands the device to the voltage-brightness relation curve of blue light electroluminescence phosphorescent devices prepared by 4DBFDPO Bright voltage is opened for 4V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 13, thus figure understands the device to the luminance-current efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 4DBFDPO Part is 3cdm in brightness-2When, current efficiency reaches maximum 6.5cdA-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 14, thus figure understands the device to the brightness-power efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 4DBFDPO Part is 3.2cdm in brightness-2When, power efficiency reaches maximum 5.2lmW-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 15, thus figure can for the current density-external quantum efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 4DBFDPO Know that the device is 0.64mAcm in brightness-2When, obtain maximum external quantum efficiency 3.4%.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 16, thus figure understands the electricity of the device to the electroluminescent light spectrogram of blue light electroluminescence phosphorescent devices prepared by 4DBFDPO Photoluminescence peak is at 462nm.
Experiment two：This experiment is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Synthetic method follow these steps to realize：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 1mmol, 1mmol anhydrous sodium acetate, The palladium of 0.001mmol and the DMF mixing of 10ml, pour into frozen water after anti-10 hours, and organic layer is obtained by extraction, and organic layer is done 1ml H are added after dry2O2Oxidation, then Jing extraction, after being dried with the volume ratio of ethanol and ethyl acetate as 1:20 is eluent post layer Analysis purifying, obtains 2,8 diphenylphosphine epoxide dibenzofurans.
Wherein the described diphenylphosphine of this experiment and the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material are 1 ︰ 1, Anhydrous sodium acetate is 1 ︰ 1, palladium and bromodiphenyl-phosphine oxygen with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material The amount ratio of base dibenzofurans material is 0.001 ︰ 1；
2, the 8 diphenylphosphine epoxide dibenzofurans that this experiment is obtained, structural formula isIts core Magnetic resonance hydrogen spectrum data be：
1H NMR(TMS,CDCl3,400MHz):=8.301 (d, J=11.6Hz, 2H), 7.796 (t, J=9.2Hz, 2H), 7.707-7.659(q,J1=6.8Hz, J2=12Hz, 10H), 7.575 (t, J=7.2Hz, 4H), 7.484ppm (t, J= 7.6Hz,8H)；LDI-TOF:M/z (%):584(100)[M+]；Elemental analysis (%) for C36H26O2P2S:C, 73.96；H,4.48；O,5.47；S,5.48；
What this experiment was obtained is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group 2,8DBFDPO。
What this experiment was obtained is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen main body material of dibenzofurans group The Ultraluminescence spectrum spectrogram of material 2,8DBFDPO is as shown in Figure 3.
The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2 based on dibenzofurans group that this experiment is obtained, The thermogravimetric analysis spectrogram of 8DBFDPO is as shown in figure 4, as seen from the figure the cracking temperature of 2,8DBFDPO is 426 DEG C.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group is (and empty as luminescent layer Cave barrier layer) it is as follows for preparing the method for electro phosphorescent device：
First, the glass substrate that Jing deionized waters are cleaned is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material NPB is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, barrier material mCP is deposited with hole transmission layer, thickness is obtained for 15nm exciton barrier-layers；
5th, n-type thermal excitation delayed fluorescence of the emitting layer material based on dibenzofurans group is deposited with exciton barrier-layer The mixture of aromatic phosphines oxygen material of main part and DMAC (dimethyl acetamide), thickness is 50nm luminescent layers；
6th, continue to be deposited with the bipolar n-type thermal excitation delayed fluorescence fragrance based on dibenzofurans group on luminescent layer Phosphine oxygen material forms hole blocking layer, and thickness is 40nm hole blocking layers；
7th, electron transport layer materials Bphen is deposited with hole blocking layer, thickness is 80nm electron transfer layers；
8th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
9th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device Part.
Metal described in step 8 is aluminium.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part in this experiment based on dibenzofurans group is both electricity The luminescent layer material of main part of phosphorescent device, is again the hole barrier layer material of electro phosphorescent device.
The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/NPB(40nm)/mCP(15nm)/2, 8DBFDPO:DMAC (20%) 50nm/2,8DBFDPO (40nm)/Bphen (80nm)/LiF (10nm)/Al.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 17, thus figure understands to be based on the voltage-current density relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFDPO The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2 of dibenzofurans group, 8DBFDPO has characteristic of semiconductor, its Threshold voltage is 3.8V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 18, thus figure understands the device to the voltage-brightness relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFDPO Bright voltage is opened for 3.8V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 19, thus figure understands the device to the luminance-current efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFDPO Part device is 83.56cdm in brightness-2When, current efficiency reaches maximum 19.75cdA-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 20, thus figure understands the device to the brightness-power efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFDPO Part device is 86.95cdm in brightness-2When, power efficiency reaches maximum 7.84lmW-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 21, thus figure can for the current density-external quantum efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFDPO Know that the device is 0.38mAcm in brightness-2When, obtain maximum external quantum efficiency 9.50%.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2, As shown in figure 22, thus figure understands the electricity of the device to the electroluminescent light spectrogram of blue light electroluminescence phosphorescent devices prepared by 8DBFDPO Photoluminescence peak is at 457nm.
Experiment three：This experiment is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Synthetic method follow these steps to realize：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 2mmol, 3mmol anhydrous sodium acetate, The palladium of 0.002mmol and the DMF mixing of 10ml, pour into frozen water after anti-10 hours, and organic layer is obtained by extraction, and organic layer is done 1ml H are added after dry2O2Oxidation, then Jing extraction, after being dried with the volume ratio of ethanol and ethyl acetate as 1:20 is eluent post layer Analysis purifying, obtains 2,4,8 diphenylphosphine epoxide dibenzofurans.
Wherein the described diphenylphosphine of this experiment and the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material are 2 ︰ 1, Anhydrous sodium acetate is 2 ︰ 1, palladium and bromodiphenyl-phosphine oxygen with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material The amount ratio of base dibenzofurans material is 0.002 ︰ 1；
2,4, the 8 diphenylphosphine epoxide dibenzofurans that this experiment is obtained, structural formula isIts core Magnetic resonance hydrogen spectrum data be：
1H NMR(TMS,CDCl3,400MHz):=8.634 (d, J=11.6Hz, 1H), 8.246 (d, J=11.6Hz, 1H), 7.843 (t, J=9.2Hz, 1H), 7.686 (t, J=12.8Hz, 9H), 7.617-7.539 (m, 11H), 7.496- 7.412ppm(m,12H)；LDI-TOF:M/z (%):784(100)[M+]；Elemental analysis (%) for C48H35O3P3S:C,73.46；H,4.50；O,6.12；P,11.84；S,4.09；
The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2 based on dibenzofurans group that this experiment is obtained, The Ultraluminescence spectrum spectrogram of 4,8DBFTPO, phosphorescence spectrum is as shown in Figure 5.
The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2 based on dibenzofurans group that this experiment is obtained, 4,8DBFTPO thermogravimetric analysis spectrogram is as shown in fig. 6, dibenzofuran group phosphine oxygen material of main part 2,4,8DBFTPO as seen from the figure Cracking temperature be 463 DEG C.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group is (and empty as luminescent layer Cave barrier layer) it is as follows for preparing the method for electro phosphorescent device：
First, the glass substrate that Jing deionized waters are cleaned is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material NPB is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, barrier material mCP is deposited with hole transmission layer, thickness is obtained for 15nm exciton barrier-layers；
5th, n-type thermal excitation delayed fluorescence of the emitting layer material based on dibenzofurans group is deposited with exciton barrier-layer The mixture of aromatic phosphines oxygen material of main part and DMAC (dimethyl acetamide), thickness is 50nm luminescent layers；
6th, continue to be deposited with the bipolar n-type thermal excitation delayed fluorescence fragrance based on dibenzofurans group on luminescent layer Phosphine oxygen material forms hole blocking layer, and thickness is 40nm hole blocking layers；
7th, electron transport layer materials Bphen is deposited with hole blocking layer, thickness is 80nm electron transfer layers；
8th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
9th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device Part.
Metal described in step 8 is aluminium.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part in this experiment based on dibenzofurans group is both electricity The luminescent layer material of main part of phosphorescent device, is again the hole barrier layer material of electro phosphorescent device.
The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/NPB(40nm)/mCP(15nm)/2,4, 8DBFTPO:DMAC (20%) 50nm/2,4,8DBFTPO (40nm)/Bphen (80nm)/LiF (10nm)/Al.This experiment is with base In blue light electroluminescence prepared by the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,8DBFTPO of dibenzofurans group As shown in figure 29, thus figure understands based on the n-type of dibenzofurans group the voltage-current density relation curve of phosphorescent devices The material of delayed fluorescence aromatic phosphines oxygen material of main part 2,4,8DBFTPO has characteristic of semiconductor, and its threshold voltage is 3.4V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 30, thus figure understands the device to the voltage-brightness relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFTPO Bright voltage is opened for 4.5V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 31, thus figure understands the device to the luminance-current efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFTPO Part brightness is 32.24cdm-2When, current efficiency reaches maximum 7.94cdA-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 32, thus figure understands the device to the brightness-power efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFTPO Part is being 37.13cdm in brightness-2When, power efficiency reaches maximum 4.52lmW-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 33, thus figure can for the current density-external quantum efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFTPO Know that the device is 0.08mAcm in brightness-2When, obtain maximum external quantum efficiency 8.26%.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 34, thus figure understands the device to the electroluminescent light spectrogram of blue light electroluminescence phosphorus phosphorescent devices prepared by 8DBFTPO Electroluminescent peak is at 462nm.
Experiment four：This experiment is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Synthetic method follow these steps to realize：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 1mmol, 1mmol anhydrous sodium acetate, The palladium of 0.002mmol and the DMF mixing of 5ml, reaction is poured into frozen water after 10 hours, and organic layer, organic layer is obtained by extraction 1ml H are added after drying2O2Oxidation, then Jing extraction, after being dried with the volume ratio of ethanol and ethyl acetate as 1:20 is eluent post Chromatographic purifying, obtains diphenylphosphine epoxide dibenzofurans for 4- bromo- 2,2 '-diphenylphosphine epoxide dibenzofurans.
Wherein the described diphenylphosphine of this experiment and the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material are 1 ︰ 1, Anhydrous sodium acetate is 1 ︰ 1, palladium and bromodiphenyl-phosphine oxygen with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material The amount ratio of base dibenzofurans material is 0.002 ︰ 1；
2,4, the 6 diphenylphosphine epoxide dibenzofurans that this experiment is obtained, structural formula is
N-type thermal excitation delayed fluorescence based on dibenzofurans group prepared by this test is detected using NMR Based on aromatic phosphines oxygen material of main part 2,4,6DBFTPO, the data of its proton nmr spectra are：
1H NMR(TMS,CDCl3,400MHz):=8.815 (d, J=11.6Hz, 1H), 8.171 (d, J=8Hz, 1H), 7.987-7.936(q,J1=7.2Hz, J2=12.4Hz, 1H), 7.676-7.629 (q, J1=7.6Hz, J2=12.4Hz, 4H), 7.587-7.495 (m, 12H), 7.486-7.332 (m, 12H), 7.287ppm (t, J=7.6Hz, 4H)；LDI-TOF:m/z (%):784(100)[M+]；Elemental analysis (%) for C48H35O3P3S:C,73.46；H,4.50；O,6.12； S,4.09；
The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2 based on dibenzofurans group that this experiment is obtained, 4,6DBFTPO Ultraluminescence spectrum spectrogram, phosphorescence spectrum is as shown in Figure 7.
What this experiment was obtained is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen main body material of dibenzofurans group The thermogravimetric analysis spectrogram of 2,4,6DBFTPO of material as schemed, shown in 8, dibenzofuran group phosphine oxygen material of main part 2,4 as seen from the figure, The cracking temperature of 6DBFTPO is 478 DEG C.
It is used for as luminescent layer based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group The method for preparing electro phosphorescent device is as follows：
First, the glass substrate that Jing deionized waters are cleaned is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode of 1～100nm Conductive layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material NPB is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, barrier material mCP is deposited with hole transmission layer, thickness is obtained for 15nm exciton barrier-layers；
5th, n-type thermal excitation delayed fluorescence of the emitting layer material based on dibenzofurans group is deposited with exciton barrier-layer The mixture of aromatic phosphines oxygen material of main part and DMAC (dimethyl acetamide), thickness is 50nm luminescent layers；
6th, continue to be deposited with based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of dibenzofurans group on luminescent layer Material forms hole blocking layer, and thickness is 40nm hole blocking layers；
7th, electron transport layer materials Bphen is deposited with hole blocking layer, thickness is 80nm electron transfer layers；
8th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
9th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device Part.
Metal described in step 8 is aluminium.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part in this experiment based on dibenzofurans group is both electricity The luminescent layer material of main part of phosphorescent device, is again the hole barrier layer material of electro phosphorescent device.
The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/NPB(40nm)/mCP(15nm)/2,4,6- DBFTPO:DMAC (20%) 50nm/2,4,6-DBFTPO (40nm)/Bphen (80nm)/LiF (10nm)/Al.This experiment is with base In blue light electroluminescence prepared by the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,6DBFTPO of dibenzofurans group As shown in figure 23, thus figure understands based on the n-type of dibenzofurans group the voltage-current density relation curve of phosphorescent devices The material of thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,6DBFTPO has characteristic of semiconductor, and its threshold voltage is 2.9V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 24, thus figure understands the device to the voltage-brightness relation curve of blue light electroluminescence phosphorescent devices prepared by 6DBFTPO Bright voltage is opened for 2.9V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 25, thus figure understands the device to the luminance-current efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 6DBFTPO Part brightness is 66.87cdm-2When, current efficiency reaches maximum 24.24cdA-1。
This experiment excites delayed fluorescence aromatic phosphines oxygen material of main part 2,4 so that the n-type based on dibenzofurans group is very hot, As shown in figure 26, thus figure understands the device to the brightness-power efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 6DBFTPO Part is 70.57cdm in brightness-2When, power efficiency reaches maximum 19.56lmW-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 27, thus figure can for the current density-external quantum efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 6DBFTPO Know that the device is 0.23mAcm in brightness-2When, obtain maximum external quantum efficiency 11.89%.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4, As shown in figure 28, thus figure understands the electricity of the device to the electroluminescent light spectrogram of blue light electroluminescence phosphorescent devices prepared by 6DBFTPO Photoluminescence peak is at 470nm.
Experiment five：This experiment is based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group Synthetic method follow these steps to realize：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 2mmol, 3mmol anhydrous sodium acetate, The palladium of 0.002mmol and the DMF mixing of 10ml, reaction is poured into frozen water after 10 hours, and organic layer, organic layer is obtained by extraction 1ml H are added after drying2O2Oxidation, then Jing extraction, after being dried with the volume ratio of ethanol and ethyl acetate as 1:20 is eluent post Chromatographic purifying, 2,4,6,8- diphenylphosphine epoxide dibenzofurans.
Wherein the described diphenylphosphine of this experiment and the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material are 2 ︰ 1, Anhydrous sodium acetate is 2 ︰ 1, palladium and bromodiphenyl-phosphine oxygen with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material The amount ratio of base dibenzofurans material is 0.002 ︰ 1；
2,4,6, the 8- diphenylphosphine epoxide dibenzofurans that this experiment is obtained, structural formula is
N-type thermal excitation delayed fluorescence based on dibenzofurans group prepared by this test is detected using NMR Aromatic phosphines oxygen material of main part 2,4,6,8DBFQPO, using NMR detect this test prepare based on dibenzofuran group The data of n-type thermal excitation delayed fluorescence base aromatic phosphines oxygen material of main part 2,4,6,8DBFQPO its proton nmr spectra of group are：
1H NMR(TMS,CDCl3,400MHz):=8.594 (d, J=11.6Hz, 2H), 7.848 (t, J=11.6Hz, 2H), 7.610-7.539 (m, 20H), 7.456 (t, J=8.4Hz, 12H), 7.345ppm (d, J=7.2Hz, 8H)；LDI-TOF: M/z (%):984(100)[M+]；Elemental analysis (%) for C60H44O4P4S:C,73.17；H,4.50；O, 6.50；S, 3.25 are tested the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part based on dibenzofurans group for obtaining The Ultraluminescence spectrum spectrogram of 2,4,6,8DBFQPO, phosphorescence spectrum is as shown in Figure 9.
The n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2 based on dibenzofurans group that this experiment is obtained, 4,6,8DBFQPO thermogravimetric analysis spectrogram is as shown in Figure 10, as seen from the figure dibenzofuran group phosphine oxygen material of main part 2, and 4,6, The cracking temperature of 8DBFQPO is 488 DEG C.
It is used for as luminescent layer based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part of dibenzofurans group The method for preparing electro phosphorescent device is as follows：
First, the glass substrate that Jing deionized waters are cleaned is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode of 1～100nm Conductive layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material NPB is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, barrier material mCP is deposited with hole transmission layer, thickness is obtained for 15nm exciton barrier-layers；
5th, n-type thermal excitation delayed fluorescence of the emitting layer material based on dibenzofurans group is deposited with exciton barrier-layer The mixture of aromatic phosphines oxygen material of main part and DMAC (dimethyl acetamide), thickness is 50nm luminescent layers；
6th, continue to be deposited with based on the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of dibenzofurans group on luminescent layer Material forms hole blocking layer, and thickness is 40nm hole blocking layers；
7th, electron transport layer materials Bphen is deposited with hole blocking layer, thickness is 80nm electron transfer layers；
8th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
9th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device Part.
Metal described in step 8 is aluminium.
N-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part in this experiment based on dibenzofurans group is both electricity The luminescent layer material of main part of phosphorescent device, is again the hole barrier layer material of electro phosphorescent device.
The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/NPB(40nm)/mCP(15nm)/2,4,6, 8DBFQPO:DMAC (20%) 50nm/2,4,6,8DBFQPO (40nm)/Bphen (80nm)/LiF (10nm)/Al.
Prepared by the dibenzofuran group phosphine oxygen material of main part 2,4,6,8DBFQPO that this experiment is modified with multifunction electroluminescent As shown in figure 35, thus figure understands dibenzofuran group phosphine oxygen main body to the voltage-current density relation curve of blue emitting phosphor device The material of material 2,4,6,8DBFQPO has characteristic of semiconductor, and its threshold voltage is 2.8V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,6, As shown in figure 36, thus figure understands the device to the voltage-brightness relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFQPO Bright voltage is opened for 3.77V.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,6, As shown in figure 37, thus figure understands the device to the luminance-current efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFQPO Part is 58.09cdm in brightness-2When, current efficiency reaches maximum 8.26cdA-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,6, As shown in figure 38, thus figure understands the device to the brightness-power efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFQPO Part is being 56.27cdm in brightness-2When, power efficiency reaches maximum 3.93lmW-1。
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,6, As shown in figure 39, thus figure can for the current density-external quantum efficiency relation curve of blue light electroluminescence phosphorescent devices prepared by 8DBFQPO Know that the device is 0.025mAcm in brightness-2When, obtain maximum external quantum efficiency 12.39%.
This experiment with based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part 2,4,6, As shown in figure 40, thus figure understands the electricity of the device to the electroluminescent light spectrogram of blue light electroluminescence phosphorescent devices prepared by 8DBFQPO Photoluminescence peak is at 467nm.

Claims (10)

1. dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part is based on, it is characterised in that the material leads to Cross and 2～4 diphenylphosphine oxygen groups compositions are introduced on 2,4,6,8 positions of dibenzofurans, molecular structural formula is as follows：
Wherein X is H or Ph2OP, Y are H or Ph2OP, Z are H or Ph2OP, and Y is H when different with Z；
When X, Y are H, Z is Ph2During OP, compound is 2,4DBFDPO, and its structural formula is：
When Y is Ph2OP, when X, Z are H, compound is 2,8DBFDPO, and its structural formula is：
When Y and Z is Ph2When OP, X are H, compound is 2,4,8DBFTPO, and its structural formula is：
When X, Y are Ph2When OP, Z are hydrogen, compound is 2,4,6DBFTPO, and its structural formula is：
When X, Y, Z are Ph2During OP, compound is 2,4,6,8DBFQPO, and its structural formula is：
2. dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part synthesis side is based on described in claim 1 Method, it is characterised in that the synthetic method is as follows：
By 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 1～6mmol, 1～6mmol anhydrous acetic acid The DMF mixing of sodium, 0.001～0.01mmol palladiums and 5～10ml, reacts 10～36 hours, and in pouring frozen water into, extraction is obtained To organic layer, after organic layer drying 1ml H are added2O2Oxidation, then Jing after extraction, being dried, it is molten with the mixing of ethanol and ethyl acetate Agent is eluent column chromatography purifying, obtains based on dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen main body material Material.
3. according to claim 2 based on the conjunction of dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part Into method, it is characterised in that the amount ratio of described diphenylphosphine and bromodiphenyl-phosphine epoxide dibenzofurans material for (1～ 2) ﹕ 1, palladium is (0.001～0.002) ﹕ 1, anhydrous acetic acid with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material Sodium is (1～2) ﹕ 1 with the amount ratio of bromodiphenyl-phosphine epoxide dibenzofurans material.
4. according to claim 2 based on the conjunction of dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part Into method, it is characterised in that ethanol and the volume ratio of ethyl acetate are 1 ﹕ 20 in the mixed solvent of the ethanol and ethyl acetate.
5. according to claim 2 based on the conjunction of dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part Into method, it is characterised in that by 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 4mmol, 4mmol nothing The DMF mixing of water sodium acetate, 0.006mmol palladiums and 6ml.
6. according to claim 2 based on the conjunction of dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part Into method, it is characterised in that by 1mmol bromodiphenyl-phosphine epoxide phenylates, the diphenylphosphine of 4mmol, 4mmol anhydrous acetic acid The DMF mixing of sodium, 0.007mmol palladiums and 7ml.
7. according to claim 2 based on the conjunction of dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part Into method, it is characterised in that by 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 5mmol, 5mmol nothing The DMF mixing of water sodium acetate, 0.009mmol palladiums and 8ml.
8. according to claim 2 based on the conjunction of dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part Into method, it is characterised in that by 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 5mmol, 5mmol nothing The DMF mixing of water sodium acetate, 0.008mmol palladiums and 9ml.
9. according to claim 2 based on the conjunction of dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part Into method, it is characterised in that by 1mmol bromodiphenyl-phosphine epoxide dibenzofurans, the diphenylphosphine of 5mmol, 5mmol nothing The DMF mixing of water sodium acetate, 0.01mmol palladiums and 10ml.
10. answering for dibenzofurans group n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material of main part is based on described in claim 1 With, it is characterised in that the n-type thermal excitation delayed fluorescence aromatic phosphines oxygen material based on dibenzofurans group is used as luminescent layer Material of main part exciton barrier-layer be used for prepare electroluminescent device.
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