CN105176520A - Preparation method and application of 4,4'-substituted benzil core-based luminescence and host material - Google Patents
Preparation method and application of 4,4'-substituted benzil core-based luminescence and host material Download PDFInfo
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Abstract
The invention belongs to the technical field of organic photoelectric materials, and discloses a preparation method and an application of a 4,4'-substituted benzil core-based luminescence and host material. The luminescent material is prepared through a Buchwald-Hartwig coupling reaction from 4,4'-dibromobenzil as an initial reaction raw material under the protection of nitrogen. The luminescent material adopts 4,4'-substituted benzil as a host structure, and the connection mode of a donor is changed to adjust the molecular weight, the pi conjugacy and eletrophilicity, the charge transfer ability and the photochromism of the material and effectively solve the carrier imbalance problem of unipolar luminescent materials. The material can be used in organic light-emitting diodes to greatly improve the external quantum efficiency of traditional fluorescent organic light-emitting diode devices.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, be specifically related to a kind of based on the luminescence of 4,4'-replacement benzil core and the preparation and application of material of main part.
Background technology
In order to improve the efficiency of organic electro-optic device, compared to polymer materials, small molecule material is determined due to structure, facilitates purifying, thus can obtain higher device efficiency, to such an extent as to may obtain commercial applications.But based on the singlet exciton of traditional organic fluorescence materials owing to usually can only utilize 25%, therefore the efficiency of device is subject to great restriction.And in the recent period, utilize thermal activation delayed fluorescence mechanism by Japanese Adachi seminar, the exciton utilization ratio of the full stress-strain material being also can reach 100%, makes the device efficiency of organic fluorescence achieve leap.But because this kind of material is due to kind, the application choice tool of kind to future thus expanding this kind of material has very important significance.Based on this mechanism small molecules redgreenblue luminescent material and prepare flexible device, for reducing the cost of material and commercial applications has unrivaled advantage, thus the R and D of novel material seem and are even more important.
Up to now, it is that there are reports for the organic light emission small molecules of core that 4,4'-replaces benzil, but extensive work concentrates on and it can be used as organic reaction intermediate, and its potentiality in Organic Light Emitting Diode have to be excavated.Meanwhile, the sensitization main body of processing using this thermal excitation delayed fluorescence material as solution does not also have relevant report.
So far Organic Light Emitting Diode has achieved considerable progress, but up to now, structure is simple and have superperformance concurrently, to meet the organic molecule luminescent material of commercialization demand still very limited, cost of development is cheap and the luminescent material of efficiency excellence still has very important meaning.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is to provide a kind of luminescence and the material of main part that replace benzil core based on 4,4'-.
Another object of the present invention is to provide a kind of above-mentioned based on the luminescence of 4,4'-replacement benzil core and the preparation method of material of main part.
Another object of the present invention is to provide the above-mentioned luminescence and the application of material of main part in organic electroluminescence device that replace benzil core based on 4,4'-.
The object of the invention is achieved through the following technical solutions:
A kind of luminescence and material of main part replacing benzil core based on 4,4'-, the molecular structure of described luminescence and material of main part is shown below:
The wherein aryl amine of Ar structural formula shown in any one of (1) ~ (17):
Preferably, described luminescent material has molecular structural formula shown any one of following P1 ~ P17:
It is above-mentioned that based on the luminescence of 4,4'-replacement benzil core and the preparation method of material of main part, described preparation method refers under nitrogen protection, is prepared by Buchwald-Hartwig linked reaction with the intermediate of structure formula (a) Suo Shi,
formula (a).
Above-mentioned luminescence and the application of material of main part in organic electroluminescence device replacing benzil core based on 4,4'-, described organic electroluminescence device comprises substrate, and is formed in anode layer on substrate, at least one luminescent layer unit and cathode layer successively; Described luminescent layer unit comprises hole injection layer, hole transmission layer, at least one luminescent layer and electron transfer layer; Described luminescent layer is at least containing a kind of above-mentioned luminescence based on 4,4 '-replacement benzil core and material of main part.
Preferably, described luminescent layer refers to red light luminescent layer or Yellow light emitting layer.
Principle of the present invention is: the luminescence and the material of main part that replace benzil structure with 4,4'-, its benzil base has very strong electron-withdrawing power, thus contributes to obtaining strong charge transfer state compound, thus obtains thermal activation delayed fluorescence compound.
Preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect:
(1) 4, the 4'-dibromo benzils that the present invention sells with the marketization are initial action raw material, obtain final product, thus for industrial applications provides possibility by simple single step reaction;
(2) materials synthesis of the present invention is simple, and structure is single, and molecular weight is determined; There is higher decomposition temperature and lower sublimation temperature, be easily sublimed into highly purified luminescent material or use as material of main part;
(3) material of the present invention is by changing to the mode of connection of body, can regulate the molecular weight of material, pi-conjugated property and Electron Affinities, charge transport ability and photochromic etc., and effectively can solve the unbalanced problem of unipolarity luminescent material current carrier;
(4) material of the present invention has good solubility, provides the possibility of solution processing, thus simplifies device making technics;
(5) material of the present invention can be applicable to Organic Light Emitting Diode, significantly can improve the external quantum efficiency of conventional fluorescent organic light emitting diode device.
Accompanying drawing explanation
Fig. 1 ~ 3 are respectively Current density-voltage-brightness curve figure, luminous efficiency-brightness-power efficiency figure and the electroluminescent spectrogram of embodiment 18 gained organic light emitting diode device;
Fig. 4 ~ 6 are respectively Current density-voltage-brightness curve figure, luminous efficiency-brightness-power efficiency figure and the electroluminescent spectrogram of embodiment 19 gained organic light emitting diode device;
Fig. 7 ~ 9 are respectively Current density-voltage-brightness curve figure, luminous efficiency-brightness-power efficiency figure and the electroluminescent spectrogram of embodiment 20 gained organic light emitting diode device;
Figure 10 ~ 12 are respectively Current density-voltage-brightness curve figure, luminous efficiency-brightness-power efficiency figure and the electroluminescent spectrogram of embodiment 21 gained organic light emitting diode device;
Figure 13 ~ 15 are respectively Current density-voltage-brightness curve figure, luminous efficiency-brightness-power efficiency figure and the electroluminescent spectrogram of embodiment 22 gained organic light emitting diode device.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The present embodiment preparation replaces luminescence and the material of main part P1 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: add 4 in 250ml there-necked flask; 4'-dibromo replaces benzil (0.368mg; 1mmol) with carbazole (367.4mg; 2.2mmol) with salt of wormwood (552mg; 4mmol) in dry toluene, under nitrogen protection, add palladium (44mg, 0.2mmol); then three tertiary butyl phosphines (0.73ml, 0.73mmol) are dripped wherein.Under nitrogen protection, heating reflux reaction 12h.Be cooled to room temperature after reaction terminates, with dichloromethane extraction, washing, crosses silicagel column with after anhydrous magnesium sulfate drying, obtains yellow solid 500mg (productive rate 90%).Molecular formula: C
38h
24n
2o
2; Molecular weight: 540.62; Ultimate analysis: C, 84.42; H, 4.47; N, 5.18; O, 5.92.
Embodiment 2
The present embodiment preparation replaces luminescence and the material of main part P2 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: add 4 in 250ml there-necked flask; 4'-dibromo replaces benzil (0.368mg; 1mmol) with tert-butyl carbazole (614mg; 2.2mmol) with salt of wormwood (552mg; 4mmol) in dry toluene, under nitrogen protection, add palladium (44mg, 0.2mmol); then three tertiary butyl phosphines (0.73ml, 0.73mmol) are dripped wherein.Under nitrogen protection, heating reflux reaction 12h.Be cooled to room temperature after reaction terminates, with dichloromethane extraction, washing, crosses silicagel column with after anhydrous magnesium sulfate drying, obtains yellow solid 700mg (productive rate 91.5%).Molecular formula: C
54h
56n
2o
2; Molecular weight: 765.05; Ultimate analysis: C, 84.78; H, 7.38; N, 3.66; O, 4.18.1HNMR(500MHz,CDCl3)δ8.31–8.26(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 preparation replaces luminescence and the material of main part P3 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), to carbazole borate ester (811mg, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains yellow solid 600mg, productive rate 86.7%.Molecular formula: C
50h
32n
2o
2; Molecular weight: 692.82; Ultimate analysis: C, 86.68; H, 4.66; N, 4.04; O, 4.62.
Embodiment 4
The present embodiment preparation replaces luminescence and the material of main part P4 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step is: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), to tert-butyl carbazole borate ester (1.06g, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains yellow solid 850mg, productive rate 92.7%.Molecular formula: C
66h
64n
2o
2; Molecular weight: 917.25; Ultimate analysis: C, 86.42; H, 7.03; N, 3.05; O, 3.49.
Embodiment 5
The present embodiment preparation replaces luminescence and the material of main part P5 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step is: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), to tert-butyl carbazole borate ester (811mg, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains yellow solid 599mg, productive rate 86.7%.Molecular formula: C
50h
32n
2o
2; Molecular weight: 692.82; Ultimate analysis: C, 86.68; H, 4.66; N, 4.04; O, 4.62.
Embodiment 6
The present embodiment preparation replaces luminescence and the material of main part P6 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step is: in 250ml there-necked flask, add 4; 4'-dibromo replaces benzil (0.368mg; 1mmol) with pentanoic (614mg; 2.2mmol) with salt of wormwood (552mg; 4mmol) in dry toluene, under nitrogen protection, add palladium (44mg, 0.2mmol); then three tertiary butyl phosphines (0.73ml, 0.73mmol) are dripped wherein.Under nitrogen protection, heating reflux reaction 12h.Be cooled to room temperature after reaction terminates, with dichloromethane extraction, washing, crosses silicagel column with after anhydrous magnesium sulfate drying, obtains yellow solid 700mg (productive rate 91.5%).Molecular formula: C
38h
28n
2o
2; Molecular weight: 544.65; Ultimate analysis: C, 83.80; H, 5.18; N, 5.14; O, 5.87.
Embodiment 7
The present embodiment preparation replaces luminescence and the material of main part P7 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: add 4 in 250ml there-necked flask; 4'-dibromo replaces benzil (0.368mg; 1mmol) with tert-butyl diphenylamine (614mg; 2.2mmol) with salt of wormwood (552mg; 4mmol) in dry toluene, under nitrogen protection, add palladium (44mg, 0.2mmol); then three tertiary butyl phosphines (0.73ml, 0.73mmol) are dripped wherein.Under nitrogen protection, heating reflux reaction 12h.Be cooled to room temperature after reaction terminates, with dichloromethane extraction, washing, crosses silicagel column with after anhydrous magnesium sulfate drying, obtains orange solids 700mg (productive rate 92%).Molecular formula: C
54h
60n
2o
2; Molecular weight: 769.09; Ultimate analysis: C, 84.33; H, 7.86; N, 3.64; O, 4.16.
Embodiment 8
The present embodiment preparation replaces luminescence and the material of main part P8 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), to pentanoic borate ester (811mg, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains yellow solid 600mg, productive rate 86.7%.Molecular formula: C
50h
36n
2o
2; Molecular weight: 696.85; Ultimate analysis: C, 86.18; H, 5.21; N, 4.02; O, 4.59.
Embodiment 9
The present embodiment preparation replaces luminescence and the material of main part P9 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), to carbazole borate ester (811mg, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains yellow solid 600mg, productive rate 86.7%.Molecular formula: C
66h
68n
2o
2; Molecular weight: 921.28; Ultimate analysis: C, 86.05; H, 7.44; N, 3.04; O, 3.47.
Embodiment 10
The present embodiment preparation replaces luminescence and the material of main part P10 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: add 4 in 250ml there-necked flask; 4'-dibromo replaces benzil (0.368mg; 1mmol) with dimethyl acridinium (460mg; 2.2mmol) with salt of wormwood (552mg; 4mmol) in dry toluene, under nitrogen protection, add palladium (44mg, 0.2mmol); then three tertiary butyl phosphines (0.73ml, 0.73mmol) are dripped wherein.Under nitrogen protection, heating reflux reaction 12h.Be cooled to room temperature after reaction terminates, with dichloromethane extraction, washing, crosses silicagel column with after anhydrous magnesium sulfate drying, obtains orange solids 500mg (productive rate 80%).Molecular formula: C
44h
36n
2o
2; Molecular weight: 624.78; Ultimate analysis: C, 84.59; H, 5.81; N, 4.48; O, 5.12.1HNMR(500MHz,CDCl3)δ8.31–8.19(m,4H),7.57–7.51(m,4H),7.48(dt,J＝11.1,5.4Hz,4H),7.08–6.97(m,8H),6.52–6.44(m,4H).1.65(s,12H)。
Embodiment 11
The present embodiment preparation replaces luminescence and the material of main part P11 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step is: in 250ml there-necked flask, add 4; 4'-dibromo replaces benzil (0.368mg; 1mmol) with Phenazoxine (403mg; 2.2mmol) with salt of wormwood (552mg; 4mmol) in dry toluene, under nitrogen protection, add palladium (44mg, 0.2mmol); then three tertiary butyl phosphines (0.73ml, 0.73mmol) are dripped wherein.Under nitrogen protection, heating reflux reaction 12h.Be cooled to room temperature after reaction terminates, with dichloromethane extraction, washing, crosses silicagel column with after anhydrous magnesium sulfate drying, obtains red solid 530mg (productive rate 75%).Molecular formula: C
38h
24n
2o
4; Molecular weight: 572.62; Ultimate analysis: C, 79.71; H, 4.22; N, 4.89; O, 11.18.1HNMR(500MHz,CDCl3)δ8.25(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 preparation replaces luminescence and the material of main part P12 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step is: in 250ml there-necked flask, add 4; 4'-dibromo replaces benzil (0.368mg; 1mmol) with thiodiphenylamine (438mg; 2.2mmol) with salt of wormwood (552mg; 4mmol) in dry toluene, under nitrogen protection, add palladium (44mg, 0.2mmol); then three tertiary butyl phosphines (0.73ml, 0.73mmol) are dripped wherein.Under nitrogen protection, heating reflux reaction 12h.Be cooled to room temperature after reaction terminates, with dichloromethane extraction, washing, crosses silicagel column with after anhydrous magnesium sulfate drying, obtains yellow solid 560mg (productive rate 92.7%).Molecular formula: C
38h
24n
2o
2s
2; Molecular weight: 604.74; Ultimate analysis: C, 75.47; H, 4.00; N, 4.63; O, 5.29; S, 10.60.1HNMR(500MHz,CDCl3)δ7.80(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 preparation replaces luminescence and the material of main part P13 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), to benzene for phenol piperazine borate ester (1.01g, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains Orange red solid 600mg, productive rate 68.6%.Molecular formula: C
62h
42n
4o
2; Molecular weight: 875.04; Ultimate analysis: C, 85.10; H, 4.84; N, 6.40; O, 3.66.
Embodiment 14
The present embodiment preparation replaces luminescence and the material of main part P14 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), dimethyl acridinium borate ester (905mg, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains Orange red solid 600mg, productive rate 77.2%.Molecular formula: C
56h
44n
2o
2; Molecular weight: 776.98; Ultimate analysis: C, 86.57; H, 5.71; N, 3.61; O, 4.12.
Embodiment 15
The present embodiment preparation replaces luminescence and the material of main part P15 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), dimethyl acridinium borate ester (845mg, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains red solid 550mg, productive rate 75.9%.Molecular formula: C
50h
32n
2o
4; Molecular weight: 724.82; Ultimate analysis: C, 82.86; H, 4.45; N, 3.86; O, 8.83.
Embodiment 16
The present embodiment preparation replaces luminescence and the material of main part P16 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), thiodiphenylamine borate ester (888mg, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains Orange red solid 610mg, productive rate 80.7%.Molecular formula: C
50h
32n
2o
2s
2; Molecular weight: 756.94; Ultimate analysis: C, 79.34; H, 4.26; N, 3.70; O, 4.23; S, 8.47.
Embodiment 17
The present embodiment preparation replaces luminescence and the material of main part P17 of benzil core based on 4,4'-, and its reaction is shown below:
Concrete implementation step: in a nitrogen atmosphere, toluene 100ml is added in 250ml flask, the wet chemical 40ml of dehydrated alcohol 30ml, 2M, 4,4'-dibromo replaces benzil (0.368mg, 1mmol), thiodiphenylamine borate ester (1.01g, 2.2mmol), then add triphenyl phosphorus palladium 200mg catalyzer, 110 DEG C are refluxed 12 hours.Be cooled to room temperature, dichloromethane extraction, anhydrous magnesium sulfate drying.Column chromatography for separation obtains Orange red solid 610mg, productive rate 80.7%.Molecular formula: C
62h
42n
4o
2; Molecular weight: 875.04; Ultimate 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)
Concrete implementation step is:
ITO transparent conducting glass supersound process in clean-out system, then use washed with de-ionized water, at acetone: ultrasonic oil removing in the mixed solvent of ethanol, is baked under a clean environment and removes moisture completely, by UV-light and ozone clean, and uses ion bombardment.
PEDOT:PSS thick for 40nm is spin-coated in pretreated clean ito glass substrate with the speed of 3000 revs/min, and dry 10min at 200 degrees celsius.Be dissolved in chlorobenzene by DBP, P2 and CBP by the mass percent of 1:15:84 is blended subsequently, go out the thick luminescent layer of 40nm with the speed spin coating of 1500 revs/min, film is annealed 10min subsequently under a nitrogen.Last TmPyPB and LiF/Al with the mode heat deposition of evaporation on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-brightness-power efficiency figure of the present embodiment gained organic light emitting diode device and electroluminescent spectrogram respectively
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)
Concrete implementation step is:
ITO transparent conducting glass supersound process in clean-out system, then use washed with de-ionized water, at acetone: ultrasonic oil removing in the mixed solvent of ethanol, is baked under a clean environment and removes moisture completely, by UV-light and ozone clean, and uses ion bombardment.
PEDOT:PSS thick for 40nm is spin-coated in pretreated clean ito glass substrate with the speed of 3000 revs/min, and dry 10min at 200 degrees celsius.Subsequently DBP and P2 is dissolved in chlorobenzene so that the mass percent of 1:99 is blended, goes out the thick luminescent layer of 40nm with the speed spin coating of 1500 revs/min, film is annealed 10min subsequently under a nitrogen.Last TmPyPB and LiF/Al with the mode heat deposition of evaporation on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-brightness-power efficiency figure of the present embodiment gained organic light emitting diode device and electroluminescent spectrogram are respectively 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)
Concrete implementation step is:
ITO transparent conducting glass supersound process in clean-out system, then use washed with de-ionized water, at acetone: ultrasonic oil removing in the mixed solvent of ethanol, is baked under a clean environment and removes moisture completely, by UV-light and ozone clean, and uses ion bombardment.
PEDOT:PSS thick for 40nm is spin-coated in pretreated clean ito glass substrate with the speed of 3000 revs/min, and dry 10min at 200 degrees celsius.Subsequently DBP and P10 is dissolved in chlorobenzene by the mass ratio of 1:99 is blended, goes out the thick luminescent layer of 40nm with the speed spin coating of 1500 revs/min, film is annealed 10min subsequently under a nitrogen.Last TmPyPB and LiF/Al with the mode heat deposition of evaporation on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-brightness-power efficiency figure of the present embodiment gained organic light emitting diode device and electroluminescent spectrogram are respectively 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)
Concrete implementation step is:
ITO transparent conducting glass supersound process in clean-out system, then use washed with de-ionized water, at acetone: ultrasonic oil removing in the mixed solvent of ethanol, is baked under a clean environment and removes moisture completely, by UV-light and ozone clean, and uses ion bombardment.
PEDOT:PSS thick for 40nm is spin-coated in pretreated clean ito glass substrate with the speed of 3000 revs/min, and dry 10min at 200 degrees celsius.Subsequently DBP, P10 and CBP are dissolved in chlorobenzene by the mass percent of 1:5:94 is blended, go out the thick luminescent layer of 40nm with the speed spin coating of 1500 revs/min, film is annealed 10min subsequently under a nitrogen.Last TmPyPB and LiF/Al with the mode heat deposition of evaporation on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-brightness-power efficiency figure of the present embodiment gained organic light emitting diode device 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)
Concrete implementation step is:
ITO transparent conducting glass supersound process in clean-out system, then use washed with de-ionized water, at acetone: ultrasonic oil removing in the mixed solvent of ethanol, is baked under a clean environment and removes moisture completely, by UV-light and ozone clean, and uses ion bombardment.
PEDOT:PSS thick for 40nm is spin-coated in pretreated clean ito glass substrate with the speed of 3000 revs/min, and dry 10min at 200 degrees celsius.Subsequently by P2 and CBP by mass percentage for the blended chlorobenzene that is dissolved in of 15:85, go out the thick luminescent layer of 40nm with the speed spin coating of 1500 revs/min, film is annealed 10min subsequently under a nitrogen.Last TmPyPB and LiF/Al with the mode heat deposition of evaporation on luminescent layer.
Current density-voltage-brightness curve figure, the luminous efficiency-brightness-power efficiency figure of the present embodiment gained organic light emitting diode device and electroluminescent spectrogram are respectively as shown in Figure 13, Figure 14 and Figure 15.
The molecular structural formula of above embodiment material therefor is as follows:
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. luminescence and the material of main part replacing benzil core based on 4,4'-, is characterized in that: the molecular structure of described luminescence and material of main part is shown below:
The wherein aryl amine of Ar structural formula shown in any one of (1) ~ (17):
2. the one according to claim 1 luminescence and the material of main part that replace benzil core based on 4,4'-, is characterized in that: the molecular structural formula shown in described luminescence and material of main part have any one of following P1 ~ P17:
3. the one described in claim 1 or 2 is based on 4; 4'-replaces the luminescence of benzil core and the preparation method of material of main part; it is characterized in that: described preparation method refers under nitrogen protection; prepared by Buchwald-Hartwig linked reaction with the intermediate of structure formula (a) Suo Shi
4. the one described in claim 1 or 2 is based on 4,4'-replaces luminescence and the application of material of main part in organic electroluminescence device of benzil core, described organic electroluminescence device comprises substrate, and is formed in anode layer on substrate, at least one luminescent layer unit and cathode layer successively; Described luminescent layer unit comprises hole injection layer, hole transmission layer, at least one luminescent layer and electron transfer layer; It is characterized in that: described luminescent layer is at least containing the luminescence and the material of main part that replace benzil core based on 4,4'-described in a kind of claim 1 or 2.
5. the one according to claim 4 luminescence and the application of material of main part in organic electroluminescence device that replace benzil core based on 4,4'-, is characterized in that: described luminescent layer refers to red light luminescent layer or Yellow light emitting layer.
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| CN112961148A (en) * | 2021-02-20 | 2021-06-15 | 电子科技大学 | Pyrazine receptor-based organic thermally-induced delayed fluorescent material and preparation method and application thereof |
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