CN104560019A - Organic blue-light luminescent material and preparation method and application thereof - Google Patents
Organic blue-light luminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of organic electroluminescent materials and discloses an organic blue-light luminescent material and a preparation method and application thereof. The material has a structural formula shown in descriptions. According to the organic blue-light luminescent material disclosed by the invention, fluorene has relatively good rigidity and planarity and good thermal stability; anthracene has high fluorescent quantum yield and is suitable for being used for preparing a blue-light material; the efficiency of organic luminescent devices based on the blue-light material is relatively high.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, particularly relate to a kind of organic blue light emitting material and its preparation method and application.
Background technology
Since the first times such as C.W.Tang report Organic Light Emitting Diode (OLED), no matter be small molecules or polymer LED, all achieved huge development.Its potential application is full color flat-panel monitor and solid-state white illumination.In three primary colours, ruddiness and green diode are all close to the requirement of practical application, but blue light material is due to greater band gap, and lower highest occupied molecular orbital (HOMO) energy level, therefore there is larger carrier injection energy barrier; Meanwhile, because emitted energy is high, unstable, easily energy trasfer occurs and cause transmitting look impure, so development is relatively slow.The blue light emitting material of research and development high-level efficiency, high stable performance, remains a difficult problem.
In the exploitation of material, have two kinds of thinkings available, one is research and develop novel blue phosphor materials, and another is the blue fluorescent material of development of new.One large advantage of fluorescent material is stable, and efficiency decay is severe unlike phosphorescent devices.Many novel blue fluorescent materials have been had to be seen in report, as: toluylene benzene class (DSA), pyridine beryllium title complex, many phenyl substituted benzene, fluorenes class, especially with spiral shell fluorene derivatives, anthracene derivative and fluorenes anthracene hybrid.Recently, Lyu etc. report the anthracene derivative that a class take tetraphenyl-silicon as core, and this compounds has higher second-order transition temperature (T
g=102 ~ 177 DEG C), and there is higher purity of color, its doping device efficiency is up to 7.5cd/A, and emission peak is at 460nm.Although many blue light materials are in the news, high-level efficiency, the material that emitting performance is stable or few.
Summary of the invention
Problem to be solved by this invention is to provide organic blue light emitting material of the higher and better heat stability of a kind of luminous efficiency.
For achieving the above object, organic blue light emitting material provided by the invention, its structure is such as formula shown:
i.e. 1,5-phenylbenzene-1,5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1,5-dihydro ring penta [def] fluorenes.
Another object of the embodiment of the present invention is to provide the preparation method of organic blue light emitting material that a kind of synthetic route is simple, material is cheap and easy to get, and described preparation method comprises the steps:
The compd A providing following structural formula to represent respectively and B,
Under oxygen-free environment, be dissolve mol ratio during the compd A of 1:2 ~ 2.4 and B are added into containing catalyzer and alkaline solution organic solvent, obtain mixing solutions, mixing solutions carries out Suzuki coupling reaction 12 ~ 48 hours at 70 ~ 130 DEG C, stopped reaction cool to room temperature, separating-purifying reaction solution, obtains described organic blue light emitting material that following structural formula represents:
Wherein, described catalyzer is organic palladium bis-triphenylphosphipalladium palladium dichloride or tetra-triphenylphosphine palladium; Or
Described catalyzer is mol ratio is the organic palladium of 1:4 ~ 8 and the mixture of organophosphorus ligand, and described organic palladium is palladium or three or two argon benzyl acetone two palladiums, described organophosphorus ligand is three (o-methyl-phenyl-) phosphines or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl; Mixture can be palladium and three (o-methyl-phenyl-) phosphine mixture or three or two argon benzyl acetone two palladiums and 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl mixture;
The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
Described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and the alkali solute in described alkaline solution and the mol ratio of compd A are 20:1.
In a preferred embodiment, organic solvent is selected from solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
In a preferred embodiment, the temperature of reaction of described Suzuki coupling reaction is 90 ~ 120 DEG C, and the reaction times is 24 ~ 36 hours.
In preferred embodiment, purified reaction liquid process also comprises step:
After Suzuki coupling reaction stops being cooled to room temperature, the organic phase extracting and obtain repeatedly also is merged with dichloromethane extraction reaction solution, then be spin-dried for after anhydrous magnesium sulfate drying organic phase, obtain crude product, crude product adopts volume ratio to be sherwood oil and the ethyl acetate mixtures of 10:1 to be leacheate to be separated through silica gel column chromatography and obtains crystalline substance, after this crystalline substance being placed in vacuum state 50 DEG C of dry 24h of environment, obtain described organic blue light emitting material.
In described preparation method, oxygen-free environment is made up of at least one gas in nitrogen, argon gas.
Above-mentioned preparation method's principle is simple, easy and simple to handle, low for equipment requirements, can wide popularization and application.
Another object of the present invention is to provide the application of above-mentioned organic blue light emitting material in organic electroluminescence device luminescent layer field.
Adopt the organic electroluminescence device that above-mentioned organic blue light emitting material is obtained, its structure comprise stack gradually substrate, anode layer, hole injection layer, hole transmission layer, luminescent layer, electric transmission/hole blocking layer, electron injecting layer and cathode layer; Wherein, the material of each functional layer is as follows:
Substrate is glass,
The material of anode layer, for adopting tin indium oxide, i.e. ITO, after ITO is combined with glass, again referred to as ito glass, or is directly called for short ITO;
The material of hole transmission layer is N, N '-two [(1-naphthyl)-N, N '-phenylbenzene]-1,1 '-xenyl-4,4 '-diamines (NPD);
The material of luminescent layer is organic blue light emitting material, namely 1,5-phenylbenzene-1,5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1,5-dihydro ring penta [def] fluorenes (representing with P) adulterates 4 of 3% mass percent, 4 '-bis-[4-(di-p-tolyl is amino) styryl] the doping mixing material that biphenyl (DPAVBi) forms, is expressed as P:DPAVBi;
The material of electric transmission/hole blocking layer is 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP);
The material of electron injecting layer is LiF;
The material of cathode layer is Al.
The structure of above-mentioned organic electroluminescence device also can be expressed as:
ITO/NPD/P:DPAVBi/BCP/LiF/Al; Wherein, brace represents laminate structure.
In organic blue light emitting material provided by the invention, fluorenes has good rigidity and planarity and good thermostability; Anthracene has high fluorescence quantum yield, is applicable to doing blue light material; Organic luminescent device efficiency based on described blue light material is higher; Meanwhile, the thermostability of this material is also better.
Separately, the preparation method of above-mentioned blue-ray organic electroluminescent material, have employed better simply synthetic route, thus reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced.
Accompanying drawing explanation
Fig. 1 is the thermogravimetic analysis (TGA) figure of organic blue light emitting material that embodiment 1 obtains;
Fig. 2 is the organic electroluminescence device structural representation that embodiment 5 obtains.
Embodiment
In order to understand the content of patent of the present invention better, technology case of the present invention is further illustrated below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein, compd A, compd B are all bought from lark prestige science and technology and are obtained.
Embodiment 1: organic blue light emitting material of the present embodiment, for: 1,5-phenylbenzene-1,5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1,5-dihydro ring penta [def] fluorenes, preparation process is as follows:
Under argon shield, 1,5-bis-(4-bromophenyl)-1,5-phenylbenzene-1,5-dihydro ring penta [def] fluorenes (128mg, 0.2mmol), 9-tetramethyl ethylene ketone boric acid ester-10-phenylanthracene (152mg, 0.4mmol) add in the flask filling 10ml toluene solvant, by salt of wormwood (2mL after abundant dissolving, 2mol/L) solution joins in flask, vacuumize deoxygenation and be filled with argon gas, then adding bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol); Flask is heated to 120 DEG C and carries out Suzuki coupling reaction 24h.Stopped reaction cool to room temperature, with dichloromethane extraction three times, then be spin-dried for after anhydrous magnesium sulfate drying organic phase, obtain crude product, crude product adopts volume ratio to be sherwood oil and the ethyl acetate mixtures of 10:1 to be leacheate to be separated through silica gel column chromatography and obtains crystalline substance, after this crystalline substance being placed in vacuum state 50 DEG C of dry 24h of environment, obtain described organic blue light emitting material.Productive rate is 73%.Mass spectrum: m/z986.4(M
++ 1); Ultimate analysis (%) C
78h
50: theoretical value: C94.90, H5.10; Measured value: C94.79, H5.24.
Fig. 1 is the thermogravimetic analysis (TGA) figure of organic blue light emitting material that embodiment 1 obtains; Thermogravimetic analysis (TGA) is completed by the measurement of Perkin-Elmer Series7 Thermo System, and all measurements all complete in atmosphere at room temperature.As shown in Figure 1, the thermal weight loss temperature (T of organic blue light emitting material 5%
d) be 417 DEG C.
Embodiment 2: organic blue light emitting material of the present embodiment, for: 1,5-phenylbenzene-1,5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1,5-dihydro ring penta [def] fluorenes, preparation process is as follows:
Under nitrogen and argon gas gas mixture are protected; by 1; 5-bis-(4-bromophenyl)-1; 5-phenylbenzene-1; 5-dihydro ring penta [def] fluorenes (192mg; 0.3mmol), 9-tetramethyl ethylene ketone boric acid ester-10-phenylanthracene (251mg; 0.66mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF); after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min; then by tetra-triphenylphosphine palladium (4mg; 0.003mmol) add wherein, after fully dissolving, add sodium bicarbonate (3mL, 2mol/L) solution again.After the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 70 DEG C and carry out Suzuki coupling reaction 48h.Stopped reaction cool to room temperature, with dichloromethane extraction three times, then be spin-dried for after anhydrous magnesium sulfate drying organic phase, obtain crude product, crude product adopts volume ratio to be sherwood oil and the ethyl acetate mixtures of 10:1 to be leacheate to be separated through silica gel column chromatography and obtains crystalline substance, after this crystalline substance being placed in vacuum state 50 DEG C of dry 24h of environment, obtain described organic blue light emitting material.Productive rate is 82%.
Embodiment 3: organic blue light emitting material of the present embodiment, for: 1,5-phenylbenzene-1,5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1,5-dihydro ring penta [def] fluorenes, preparation process is as follows:
Under nitrogen protection, by 1,5-bis-(4-bromophenyl)-1,5-phenylbenzene-1,5-dihydro ring penta [def] fluorenes (192mg, 0.3mmol), 9-tetramethyl ethylene ketone boric acid ester-10-phenylanthracene (274mg, 0.72mmol), palladium (3.5mg, 0.015mmol) He three (o-methyl-phenyl-) phosphine (21mg, 0.06mmol) join in the flask of the DMF filling 12mL, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution, after in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 130 DEG C and carries out Suzuki coupling reaction 12h.Stopped reaction cool to room temperature, with dichloromethane extraction three times, then be spin-dried for after anhydrous magnesium sulfate drying organic phase, obtain crude product, crude product adopts volume ratio to be sherwood oil and the ethyl acetate mixtures of 10:1 to be leacheate to be separated through silica gel column chromatography and obtains crystalline substance, after this crystalline substance being placed in vacuum state 50 DEG C of dry 24h of environment, obtain described organic blue light emitting material.Productive rate is 86%.
Embodiment 4: organic blue light emitting material of the present embodiment, for: 1,5-phenylbenzene-1,5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1,5-dihydro ring penta [def] fluorenes, preparation process is as follows:
Under nitrogen protection; by 1; 5-bis-(4-bromophenyl)-1; 5-phenylbenzene-1; 5-dihydro ring penta [def] fluorenes (192mg; 0.3mmol), 9-tetramethyl ethylene ketone boric acid ester-10-phenylanthracene (274mg; 0.72mmol), three or two argon benzyl acetone two palladium (9mg; 0.009mmol) with 2-dicyclohexyl phosphine-2 '; 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins in the flask of the DMF filling 12mL; sodium carbonate (3mL, 2mol/L) solution is added after abundant dissolving.After in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 90 DEG C and carries out Suzuki coupling reaction 36h.Stopped reaction cool to room temperature, with dichloromethane extraction three times, then be spin-dried for after anhydrous magnesium sulfate drying organic phase, obtain crude product, crude product adopts volume ratio to be sherwood oil and the ethyl acetate mixtures of 10:1 to be leacheate to be separated through silica gel column chromatography and obtains crystalline substance, after this crystalline substance being placed in vacuum state 50 DEG C of dry 24h of environment, obtain described organic blue light emitting material.Productive rate is 87%.
Embodiment 5:
The present embodiment is organic electroluminescence device, its organic blue light emitting material obtained with the present invention, i.e. 1,5-phenylbenzene-1,5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1,5-dihydro ring penta [def] fluorenes is as the material of main part of luminescent layer.
As shown in Figure 2, this organic electroluminescence device comprises the substrate layer 1(ITO be made up of substrate of glass and the anode layer that is deposited on substrate of glass one surface and represents), hole transmission layer 2(material is N, N '-two [(1-naphthyl)-N, N '-phenylbenzene]-1, 1 '-xenyl-4, 4 '-diamines (NPD)), luminescent layer 3(material is 1, 5-phenylbenzene-1, 5-bis-(4-(10-phenylanthracene-9-base) phenyl)-1, 5-dihydro ring penta [def] fluorenes (representing with P) adulterates 4 of 3% mass percent, the doping mixing material that 4 '-bis-[4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) forms, be expressed as P:DPAVBi), (material is 2 to electric transmission/hole blocking layer 4, 9-dimethyl-4, 7-phenylbenzene-1, 10-phenanthroline (BCP)), electron injecting layer 5(material is LiF) and cathode layer 6(material be Al).
The concrete grammar that this organic electroluminescence device makes is:
First, on anode layer (ITO) surface of the substrate layer through cleaning, hot evaporation process is adopted, successively evaporation hole transmission layer (NPD), luminescent layer, electric transmission/hole blocking layer (BCP), electron injecting layer (LiF) and cathode layer (Al);
After above-mentioned technique is complete, obtained organic electroluminescence device.
The structure of this organic electroluminescence device can be expressed as: ITO(150nm)/NPD (20nm)/P:DPAVBi(20nm)/BCP (30nm)/LiF (1.5nm)/Al (150nm); Wherein, the thickness of each functional layer of numeric representation in bracket.
Test the current versus brightness-voltage characteristic of this organic electroluminescence device, test completes by with Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) correcting silicon photoelectric diode; Test result is: the trigger voltage of organic electroluminescence device is 4.3V, at 1000cd/m
2brightness under, luminous efficiency is 3.6lm/W.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic blue light emitting material, is characterized in that, its structural formula is as follows:
2. a preparation method for organic blue light emitting material as claimed in claim 1, is characterized in that, its following steps:
The compd A providing following structural formula to represent respectively and B,
Under oxygen-free environment, be dissolve mol ratio during the compd A of 1:2 ~ 2.4 and compd B are added into containing catalyzer and alkaline solution organic solvent, obtain mixing solutions; This mixing solutions carried out Suzuki coupling reaction after 12 ~ 48 hours at 70 ~ 130 DEG C, stopped reaction cool to room temperature, and purified reaction liquid, obtaining structural formula is
described organic blue light emitting material.
3. the preparation method of organic blue light emitting material according to claim 2, is characterized in that, described catalyzer is bis-triphenylphosphipalladium palladium dichloride or tetra-triphenylphosphine palladium, and the mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
4. the preparation method of organic blue light emitting material according to claim 2, it is characterized in that, described catalyzer is mol ratio is the organic palladium of 1:4 ~ 8 and the mixture of organophosphorus ligand, and the mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
5. the preparation method of organic blue light emitting material according to claim 4, it is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums, and described organophosphorus ligand is three (o-methyl-phenyl-) phosphines or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.
6. the preparation method of organic blue light emitting material according to claim 2, it is characterized in that, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and the alkali solute in described alkaline solution and the mol ratio of compd A are 20:1.
7. the preparation method of organic blue light emitting material according to claim 2, is characterized in that, it is at least one in toluene, DMF, tetrahydrofuran (THF) that described organic solvent is selected from solvent.
8. the preparation method of organic blue light emitting material according to claim 2, is characterized in that, the temperature of reaction of described Suzuki coupling reaction is 90 ~ 120 DEG C, and the reaction times is 24 ~ 36 hours.
9., according to the preparation method of the arbitrary described organic blue light emitting material of claim 2 to 8, it is characterized in that, purified reaction liquid process also comprises step:
After Suzuki coupling reaction stops being cooled to room temperature, the organic phase extracting and obtain repeatedly also is merged with dichloromethane extraction reaction solution, then be spin-dried for after anhydrous magnesium sulfate drying organic phase, obtain crude product, crude product adopts volume ratio to be sherwood oil and the ethyl acetate mixtures of 10:1 to be leacheate to be separated through silica gel column chromatography and obtains crystalline substance, after this crystalline substance being placed in vacuum state 50 DEG C of dry 24h of environment, obtain described organic blue light emitting material.
10. the application of organic blue light emitting material according to claim 1 in organic electroluminescence device luminescent layer field.
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