CN105176520B - One kind is based on 4,4′The preparation and application of the luminous and material of main part of substitution benzil core - Google Patents
One kind is based on 4,4′The preparation and application of the luminous and material of main part of substitution benzil core Download PDFInfo
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Abstract
The invention belongs to organic photoelectrical material technical field, a kind of preparation and application of the luminous and material of main part based on 4,4' substitution benzil cores are disclosed.Luminescent material of the invention is, for initial action raw material, under nitrogen protection, to be prepared by Buchwald Hartwig coupling reactions with 4,4' dibromos benzil.Luminescent material of the invention is with 4,4' substitution benzils are agent structure, by changing the connected mode of donor, the molecular weight of material, pi-conjugated property and electrophilicity, charge transport ability and photochromic etc. can be adjusted, and can effectively solve the problem that the unipolarity unbalanced problem of luminescent material carrier.It is applied to Organic Light Emitting Diode, can greatly improve the external quantum efficiency of conventional fluorescent organic light emitting diode device.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, and in particular to one kind replaces the hair of benzil core based on 4,4'-
The preparation and application of light and material of main part.
Background technology
In order to improve the efficiency of organic electro-optic device, for polymeric material, small molecule material is true due to structure
It is fixed, convenient purifying, thus device efficiency higher can be obtained, so that being likely to be obtained commercial applications.But based on tradition
Organic fluorescence materials due to being typically only capable to the singlet exciton using 25%, therefore the efficiency of device is extremely limited.
And it is recent, thermal activation delayed fluorescence mechanism, the exciton utilization rate of the full stress-strain material for being are utilized by Japanese Adachi seminars
100% can also be reached so that the device efficiency of organic fluorescence realizes leap.Yet with this kind of material due to species, because
And the species for expanding this kind of material has very important significance to following application selection tool.Small molecule RGB based on this mechanism
Three-colour light-emitting material simultaneously prepares flexible device, and the cost and commercial applications for reducing material have unrivaled advantage,
The thus R and D of new material seem and are even more important.
Up to now, there are reports for the organic light emission small molecule of core for 4,4'- substitution benzils, but extensive work
Concentrate on as organic reaction intermediate, its potentiality in Organic Light Emitting Diode has to be excavated.Meanwhile, with this heat shock
Hair delayed fluorescence material is used as the also no relevant report of sensitization main body that solution is processed.
So far Organic Light Emitting Diode has been achieved for considerable progress, but up to now, simple structure and has concurrently good
Good performance, the organic molecule luminescent material for meeting commercialization demand are still extremely limited, and development cost is cheap and efficiency is excellent
Luminescent material still there is very important meaning.
The content of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the invention is to provide one kind to be based on
The luminous and material of main part of 4,4'- substitution benzil cores.
Another object of the present invention is to provide a kind of above-mentioned luminous and material of main part based on 4,4'- substitution benzil cores
Preparation method.
A further object of the present invention is to provide the above-mentioned luminous and material of main part based on 4,4'- substitution benzil cores having
Application in organic electroluminescence devices.
The object of the invention is achieved through the following technical solutions：
Luminous and material of main part of the one kind based on 4,4'- substitution benzil cores, the molecule knot of the luminous and material of main part
Structure is shown below：
Wherein Ar is the aryl amine of any one of (1)~(17) shown structural formula：
Preferably, the luminescent material has the shown molecular structural formulas of any one of following P1~P17：
Above-mentioned to be based on the preparation method that 4,4'- replaces the luminous and material of main part of benzil core, the preparation method refers to
Under nitrogen protection, prepared by Buchwald-Hartwig coupling reactions with the intermediate of structure shown in formula (a),
Formula (a).
Above-mentioned luminous and application of the material of main part in organic electroluminescence device for being based on 4,4'- substitution benzil cores,
The organic electroluminescence device includes substrate, and is sequentially formed at anode layer, at least one luminescent layer unit on substrate
And cathode layer；Described luminescent layer unit includes hole injection layer, hole transmission layer, at least one luminescent layer and electric transmission
Layer；Described luminescent layer at least contains a kind of above-mentioned luminous and material of main part for being based on 4,4 '-substitution benzil core.
Preferably, described luminescent layer refers to red light luminescent layer or Yellow light emitting layer.
Principle of the invention is：With the luminous and material of main part of 4,4'- substitution benzil structures, its benzil base has very
Strong electron-withdrawing power, thus helps in and obtains strong charge transfer state compound, so as to obtain thermal activation delayed fluorescence chemical combination
Thing.
Preparation method of the invention and resulting product have the following advantages that and beneficial effect：
(1) 4, the 4'- dibromos benzil with marketization sale of the invention is anti-by a simple step for initial action raw material
Final product should be obtained, thus for industrial applications provide possibility；
(2) materials synthesis of the present invention are simple, and structure is single, and molecular weight determines；With decomposition temperature higher and than relatively low
Sublimation temperature, be easily sublimed into the luminescent material of high-purity or used as material of main part；
(3) material of the invention is by changing the connected mode of donor, can adjust the molecular weight of material, pi-conjugated property and
Electrophilicity, charge transport ability and photochromic etc., and can effectively solve the problem that the unipolarity unbalanced problem of luminescent material carrier；
(4) material of the invention has good dissolubility, there is provided the possibility of solution processing, so as to simplify device system
Make technique；
(5) material of the invention can be applied to Organic Light Emitting Diode, can greatly improve conventional fluorescent organic light-emitting diodes
The external quantum efficiency of tube device.
Brief description of the drawings
Fig. 1~3 be respectively the gained organic light emitting diode device of embodiment 18 Current density-voltage-brightness curve figure,
Luminous efficiency-brightness-power efficiency figure and electroluminescent spectrogram；
Fig. 4~6 be respectively the gained organic light emitting diode device of embodiment 19 Current density-voltage-brightness curve figure,
Luminous efficiency-brightness-power efficiency figure and electroluminescent spectrogram；
Fig. 7~9 be respectively the gained organic light emitting diode device of embodiment 20 Current density-voltage-brightness curve figure,
Luminous efficiency-brightness-power efficiency figure and electroluminescent spectrogram；
Figure 10~12 are respectively the Current density-voltage-brightness curve of the gained organic light emitting diode device of embodiment 21
Figure, luminous efficiency-brightness-power efficiency figure and electroluminescent spectrogram；
Figure 13~15 are respectively the Current density-voltage-brightness curve of the gained organic light emitting diode device of embodiment 22
Figure, luminous efficiency-brightness-power efficiency figure and electroluminescent spectrogram.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
The present embodiment prepares the luminous and material of main part P1 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step：4,4'- dibromos are added to replace benzil (0.368mg, 1mmol) in 250ml there-necked flasks
In carbazole (367.4mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene, nitrogen protection is lower to add palladium
(44mg, 0.2mmol), is then added dropwise three tertiary butyl phosphines (0.73ml, 0.73mmol) thereto.Under nitrogen protection, heat back
Stream reaction 12h.Reaction is cooled to room temperature after terminating, and is extracted with dichloromethane, washing, and silica gel is crossed after being dried with anhydrous magnesium sulfate
Post, obtains yellow solid 500mg (yield 90%).Molecular formula:C38H24N2O2；Molecular weight：540.62；Elementary analysis：C,
84.42；H,4.47；N,5.18；O,5.92.
Embodiment 2
The present embodiment prepares the luminous and material of main part P2 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step：4,4'- dibromos are added to replace benzil (0.368mg, 1mmol) in 250ml there-necked flasks
In tert-butyl carbazole (614mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene, nitrogen protection is lower to add vinegar
Sour palladium (44mg, 0.2mmol), is then added dropwise three tertiary butyl phosphines (0.73ml, 0.73mmol) thereto.Under nitrogen protection, plus
Hot back flow reaction 12h.Reaction is cooled to room temperature after terminating, and is extracted with dichloromethane, washing, and silicon is crossed after being dried with anhydrous magnesium sulfate
Glue post, obtains yellow solid 700mg (yield 91.5%).Molecular formula:C54H56N2O2；Molecular weight：765.05；Elementary analysis：C,
84.78；H,7.38；N,3.66；O,4.18.1H NMR (500MHz, CDCl3) δ 8.31-8.26 (m, 4H), 8.14 (t, J=
1.2Hz,4H),7.83–7.79(m,4H),7.52–7.46(m,8H),1.51–1.43(m,36H)。
Embodiment 3
The present embodiment prepares the luminous and material of main part P3 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), to carbazole borate ester (811mg,
2.2mmol), triphenyl phosphorus palladium 200mg catalyst is subsequently adding, 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloromethane extraction
Take, anhydrous magnesium sulfate is dried.Column chromatography for separation obtains yellow solid 600mg, yield 86.7%.Molecular formula：C50H32N2O2；Molecule
Amount：692.82；Elementary analysis：C,86.68；H,4.66；N,4.04；O,4.62.
Embodiment 4
The present embodiment prepares the luminous and material of main part P4 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step is：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml in 250ml flasks,
The wet chemical 40ml of 2M, 4,4'- dibromos replace benzil (0.368mg, 1mmol), to tert-butyl carbazole borate ester
(1.06g, 2.2mmol), is subsequently adding triphenyl phosphorus palladium 200mg catalyst, and 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloro
Methane is extracted, and anhydrous magnesium sulfate is dried.Column chromatography for separation obtains yellow solid 850mg, yield 92.7%.Molecular formula：C66H64N2O2；
Molecular weight：917.25；Elementary analysis：C,86.42；H,7.03；N,3.05；O,3.49.
Embodiment 5
The present embodiment prepares the luminous and material of main part P5 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step is：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml in 250ml flasks,
The wet chemical 40ml of 2M, 4,4'- dibromos replace benzil (0.368mg, 1mmol), to tert-butyl carbazole borate ester
(811mg, 2.2mmol), is subsequently adding triphenyl phosphorus palladium 200mg catalyst, and 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloro
Methane is extracted, and anhydrous magnesium sulfate is dried.Column chromatography for separation obtains yellow solid 599mg, yield 86.7%.Molecular formula：C50H32N2O2；
Molecular weight：692.82；Elementary analysis：C,86.68；H,4.66；N,4.04；O,4.62.
Embodiment 6
The present embodiment prepares the luminous and material of main part P6 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step is：Added in 250ml there-necked flasks 4,4'- dibromos replace benzil (0.368mg,
1mmol) and diphenylamines (614mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) are in dry toluene, the lower addition of nitrogen protection
Palladium (44mg, 0.2mmol), is then added dropwise three tertiary butyl phosphines (0.73ml, 0.73mmol) thereto.Under nitrogen protection,
Heating reflux reaction 12h.Reaction is cooled to room temperature after terminating, and is extracted with dichloromethane, washing, mistake after being dried with anhydrous magnesium sulfate
Silicagel column, obtains yellow solid 700mg (yield 91.5%).Molecular formula:C38H28N2O2；Molecular weight：544.65；Elementary analysis：
C,83.80；H,5.18；N,5.14；O,5.87.
Embodiment 7
The present embodiment prepares the luminous and material of main part P7 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step：4,4'- dibromos are added to replace benzil (0.368mg, 1mmol) in 250ml there-necked flasks
In tert-butyl diphenylamine (614mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene, nitrogen protection is lower to be added
Palladium (44mg, 0.2mmol), is then added dropwise three tertiary butyl phosphines (0.73ml, 0.73mmol) thereto.Under nitrogen protection,
Heating reflux reaction 12h.Reaction is cooled to room temperature after terminating, and is extracted with dichloromethane, washing, mistake after being dried with anhydrous magnesium sulfate
Silicagel column, obtains orange solids 700mg (yield 92%).Molecular formula:C54H60N2O2；Molecular weight：769.09；Elementary analysis：C,
84.33；H,7.86；N,3.64；O,4.16.
Embodiment 8
The present embodiment prepares the luminous and material of main part P8 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), to diphenylamines borate ester (811mg,
2.2mmol), triphenyl phosphorus palladium 200mg catalyst is subsequently adding, 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloromethane extraction
Take, anhydrous magnesium sulfate is dried.Column chromatography for separation obtains yellow solid 600mg, yield 86.7%.Molecular formula：C50H36N2O2；Molecule
Amount：696.85；Elementary analysis：C,86.18；H,5.21；N,4.02；O,4.59.
Embodiment 9
The present embodiment prepares the luminous and material of main part P9 based on 4,4'- substitution benzil cores, and its reaction is shown below：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), to carbazole borate ester (811mg,
2.2mmol), triphenyl phosphorus palladium 200mg catalyst is subsequently adding, 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloromethane extraction
Take, anhydrous magnesium sulfate is dried.Column chromatography for separation obtains yellow solid 600mg, yield 86.7%.Molecular formula：C66H68N2O2；Molecule
Amount：921.28；Elementary analysis：C,86.05；H,7.44；N,3.04；O,3.47.
Embodiment 10
The present embodiment prepares the luminous and material of main part P10 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step：4,4'- dibromos are added to replace benzil (0.368mg, 1mmol) in 250ml there-necked flasks
In dimethyl acridinium (460mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) to dry toluene, nitrogen protection is lower to add vinegar
Sour palladium (44mg, 0.2mmol), is then added dropwise three tertiary butyl phosphines (0.73ml, 0.73mmol) thereto.Under nitrogen protection, plus
Hot back flow reaction 12h.Reaction is cooled to room temperature after terminating, and is extracted with dichloromethane, washing, and silicon is crossed after being dried with anhydrous magnesium sulfate
Glue post, obtains orange solids 500mg (yield 80%).Molecular formula:C44H36N2O2；Molecular weight：624.78；Elementary analysis：C,
84.59；H,5.81；N,4.48；O,5.12.1H NMR(500MHz,CDCl3)δ8.31–8.19(m,4H),7.57–7.51(m,
4H), (m, the 4H) .1.65 (s, 12H) of 7.48 (dt, J=11.1,5.4Hz, 4H), 7.08-6.97 (m, 8H), 6.52-6.44.
Embodiment 11
The present embodiment prepares the luminous and material of main part P11 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step is：Added in 250ml there-necked flasks 4,4'- dibromos replace benzil (0.368mg,
1mmol) and phenoxazine (403mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) are in dry toluene, the lower addition of nitrogen protection
Palladium (44mg, 0.2mmol), is then added dropwise three tertiary butyl phosphines (0.73ml, 0.73mmol) thereto.Under nitrogen protection,
Heating reflux reaction 12h.Reaction is cooled to room temperature after terminating, and is extracted with dichloromethane, washing, mistake after being dried with anhydrous magnesium sulfate
Silicagel column, obtains red solid 530mg (yield 75%).Molecular formula:C38H24N2O4；Molecular weight：572.62；Elementary analysis：C,
79.71；H,4.22；N,4.89；O,11.18.1H NMR (500MHz, CDCl3) δ 8.25 (d, J=8.0Hz, 4H), 7.57 (d, J
=8.1Hz, 4H), 6.74 (dd, J=14.9,7.2Hz, 8H), 6.64 (t, J=7.2Hz, 4H), 6.05 (d, J=7.7Hz,
4H)。
Embodiment 12
The present embodiment prepares the luminous and material of main part P12 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step is：Added in 250ml there-necked flasks 4,4'- dibromos replace benzil (0.368mg,
1mmol) and phenthazine (438mg, 2.2mmol) and potassium carbonate (552mg, 4mmol) are in dry toluene, the lower addition of nitrogen protection
Palladium (44mg, 0.2mmol), is then added dropwise three tertiary butyl phosphines (0.73ml, 0.73mmol) thereto.Under nitrogen protection,
Heating reflux reaction 12h.Reaction is cooled to room temperature after terminating, and is extracted with dichloromethane, washing, mistake after being dried with anhydrous magnesium sulfate
Silicagel column, obtains yellow solid 560mg (yield 92.7%).Molecular formula:C38H24N2O2S2；Molecular weight：604.74；Element point
Analysis：C,75.47；H,4.00；N,4.63；O,5.29；S,10.60.1H NMR (500MHz, CDCl3) δ 7.80 (d, J=9.0Hz,
4H), 7.45-7.41 (m, 4H), 7.33-7.27 (m, 8H), 7.19 (t, J=5.9Hz, 4H), 7.06 (t, J=8.9Hz, 4H).
Embodiment 13
The present embodiment prepares the luminous and material of main part P13 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), to benzene for phenol piperazine borate ester
(1.01g, 2.2mmol), is subsequently adding triphenyl phosphorus palladium 200mg catalyst, and 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloro
Methane is extracted, and anhydrous magnesium sulfate is dried.Column chromatography for separation obtains Orange red solid 600mg, yield 68.6%.Molecular formula：
C62H42N4O2；Molecular weight：875.04；Elementary analysis：C,85.10；H,4.84；N,6.40；O,3.66.
Embodiment 14
The present embodiment prepares the luminous and material of main part P14 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), dimethyl acridinium borate ester
(905mg, 2.2mmol), is subsequently adding triphenyl phosphorus palladium 200mg catalyst, and 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloro
Methane is extracted, and anhydrous magnesium sulfate is dried.Column chromatography for separation obtains Orange red solid 600mg, yield 77.2%.Molecular formula：
C56H44N2O2；Molecular weight：776.98；Elementary analysis：C,86.57；H,5.71；N,3.61；O,4.12.
Embodiment 15
The present embodiment prepares the luminous and material of main part P15 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), dimethyl acridinium borate ester
(845mg, 2.2mmol), is subsequently adding triphenyl phosphorus palladium 200mg catalyst, and 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloro
Methane is extracted, and anhydrous magnesium sulfate is dried.Column chromatography for separation obtains red solid 550mg, yield 75.9%.Molecular formula：C50H32N2O4；
Molecular weight：724.82；Elementary analysis：C,82.86；H,4.45；N,3.86；O,8.83.
Embodiment 16
The present embodiment prepares the luminous and material of main part P16 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), phenthazine borate ester (888mg,
2.2mmol), triphenyl phosphorus palladium 200mg catalyst is subsequently adding, 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloromethane extraction
Take, anhydrous magnesium sulfate is dried.Column chromatography for separation obtains Orange red solid 610mg, yield 80.7%.Molecular formula：C50H32N2O2S2；Point
Son amount：756.94；Elementary analysis：C,79.34；H,4.26；N,3.70；O,4.23；S,8.47.
Embodiment 17
The present embodiment prepares the luminous and material of main part P17 based on 4,4'- substitution benzil cores, and its reaction is such as following formula institute
Show：
Specific implementation step：In a nitrogen atmosphere, toward addition toluene 100ml, absolute ethyl alcohol 30ml, 2M in 250ml flasks
Wet chemical 40ml, 4,4'- dibromos replace benzil (0.368mg, 1mmol), phenthazine borate ester (1.01g,
2.2mmol), triphenyl phosphorus palladium 200mg catalyst is subsequently adding, 110 DEG C are flowed back 12 hours.It is cooled to room temperature, dichloromethane extraction
Take, anhydrous magnesium sulfate is dried.Column chromatography for separation obtains Orange red solid 610mg, yield 80.7%.Molecular formula：C62H42N4O2；Molecule
Amount：875.04；Elementary analysis：C,85.10；H,4.84；N,6.40；O,3.66.
Embodiment 18
A kind of Organic Light Emitting Diode of the present embodiment, device architecture is as follows：
ITO(125nm)/PEDOT:PSS (40)/1wt%DBP:15wt%
P2:CBP(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)
Specific implementation step is：
Transparent electro-conductive glass is ultrasonically treated in cleaning agent, then is cleaned with deionized water, in acetone：The mixing of ethanol
Ultrasonic oil removing, is baked to removes moisture completely under a clean environment in solvent, with ultraviolet light and ozone clean, and with ion Hong
Hit.
By the thick PEDOT of 40nm：PSS is spin-coated on the clean ito glass substrate of pretreatment with 3000 revs/min of speed
On, and 10min is dried at 200 degrees celsius.DBP, P2 and CBP are then pressed 1:15:84 mass percent blending is dissolved in chlorine
In benzene, the thick luminescent layers of 40nm are gone out with 1500 revs/min of speed spin coating, film is then annealed 10min under a nitrogen.Finally
TmPyPB and LiF/Al in the way of being deposited with heat deposition on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-bright of the present embodiment gained organic light emitting diode device
Degree-power efficiency figure and electroluminescent spectrogram respectively as shown in Figure 1, Figure 2 and Figure 3.
Embodiment 19
A kind of Organic Light Emitting Diode of the present embodiment, device architecture is as follows：
ITO(125nm)/PEDOT:PSS (40nm)/1wt%DBP:99wt%P2
(40nm)/TmPyPB(50)/LiF(1nm)/Al(100nm)
Specific implementation step is：
Transparent electro-conductive glass is ultrasonically treated in cleaning agent, then is cleaned with deionized water, in acetone：The mixing of ethanol
Ultrasonic oil removing, is baked to removes moisture completely under a clean environment in solvent, with ultraviolet light and ozone clean, and with ion Hong
Hit.
By the thick PEDOT of 40nm：PSS is spin-coated on the clean ito glass substrate of pretreatment with 3000 revs/min of speed
On, and 10min is dried at 200 degrees celsius.Then by DBP and P2 with 1:99 mass percent blending is dissolved in chlorobenzene, with
1500 revs/min of speed spin coating goes out the thick luminescent layers of 40nm, and film is then annealed 10min under a nitrogen.Last TmPyPB and
LiF/Al in the way of being deposited with heat deposition on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-bright of the present embodiment gained organic light emitting diode device
Degree-power efficiency figure and electroluminescent spectrogram difference are as shown in Figure 4, Figure 5 and Figure 6.
Embodiment 20
A kind of Organic Light Emitting Diode of the present embodiment, device architecture is as follows：
ITO(125nm)/PEDOT:PSS (40nm)/1wt%DBP:99wt%P10
(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)
Specific implementation step is：
Transparent electro-conductive glass is ultrasonically treated in cleaning agent, then is cleaned with deionized water, in acetone：The mixing of ethanol
Ultrasonic oil removing, is baked to removes moisture completely under a clean environment in solvent, with ultraviolet light and ozone clean, and with ion Hong
Hit.
By the thick PEDOT of 40nm：PSS is spin-coated on the clean ito glass substrate of pretreatment with 3000 revs/min of speed
On, and 10min is dried at 200 degrees celsius.DBP and P10 is then pressed 1:99 mass ratio blending is dissolved in chlorobenzene, with 1500
Rev/min speed spin coating go out the thick luminescent layers of 40nm, film is then annealed 10min under a nitrogen.Last TmPyPB and LiF/
Al in the way of being deposited with heat deposition on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-bright of the present embodiment gained organic light emitting diode device
Degree-power efficiency figure and electroluminescent spectrogram difference are as shown in Figure 7, Figure 8 and Figure 9.
Embodiment 21
A kind of Organic Light Emitting Diode of the present embodiment, device architecture is as follows：
ITO(125nm)/PEDOT:PSS (40nm)/1wt%DBP:5%P10:94wt%CBP
(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)
Specific implementation step is：
Transparent electro-conductive glass is ultrasonically treated in cleaning agent, then is cleaned with deionized water, in acetone：The mixing of ethanol
Ultrasonic oil removing, is baked to removes moisture completely under a clean environment in solvent, with ultraviolet light and ozone clean, and with ion Hong
Hit.
By the thick PEDOT of 40nm：PSS is spin-coated on the clean ito glass substrate of pretreatment with 3000 revs/min of speed
On, and 10min is dried at 200 degrees celsius.DBP, P10 and CBP are then pressed 1:5:94 mass percent blending is dissolved in chlorine
Benzene, the thick luminescent layers of 40nm are gone out with 1500 revs/min of speed spin coating, and film is then annealed 10min under a nitrogen.Finally
TmPyPB and LiF/Al in the way of being deposited with heat deposition on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-bright of the present embodiment gained organic light emitting diode device
Degree-power efficiency figure and electroluminescent spectrogram are respectively as shown in Figure 10, Figure 11 and Figure 12.
Embodiment 22
A kind of Organic Light Emitting Diode of the present embodiment, device architecture is as follows：
ITO(125nm)/PEDOT:PSS (40nm)/15%P2：85wt%CBP
(40nm)/TmPyPB(50nm)/LiF(1nm)/Al(100nm)
Specific implementation step is：
Transparent electro-conductive glass is ultrasonically treated in cleaning agent, then is cleaned with deionized water, in acetone：The mixing of ethanol
Ultrasonic oil removing, is baked to removes moisture completely under a clean environment in solvent, with ultraviolet light and ozone clean, and with ion Hong
Hit.
By the thick PEDOT of 40nm：PSS is spin-coated on the clean ito glass substrate of pretreatment with 3000 revs/min of speed
On, and 10min is dried at 200 degrees celsius.It is then by mass percentage 15 by P2 and CBP:85 blendings are dissolved in chlorobenzene, with
1500 revs/min of speed spin coating goes out the thick luminescent layers of 40nm, and film is then annealed 10min under a nitrogen.Last TmPyPB and
LiF/Al in the way of being deposited with heat deposition on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-bright of the present embodiment gained organic light emitting diode device
Degree-power efficiency figure and electroluminescent spectrogram are respectively as shown in Figure 13, Figure 14 and Figure 15.
The molecular structural formula of above example material therefor is as follows：
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (2)
1. a kind of luminous and application of the material of main part in organic electroluminescence device, institute based on 4,4'- substitution benzil cores
Organic electroluminescence device is stated including substrate, and be sequentially formed at anode layer on substrate, at least one luminescent layer unit and
Cathode layer；Described luminescent layer unit includes hole injection layer, hole transmission layer, at least one luminescent layer and electron transfer layer；
It is characterized in that：Described luminescent layer at least contains a kind of luminous and material of main part based on 4,4'- substitution benzil cores；It is described
Luminous and material of main part based on 4,4'- substitution benzil cores has the shown molecular structural formulas of any one of following P1~P17：
2. a kind of luminous and material of main part based on 4,4'- substitution benzil cores according to claim 1 is in organic electroluminescence
Application in luminescent device, it is characterised in that：Described luminescent layer refers to red light luminescent layer or Yellow light emitting layer.
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