CN104448248A - Organic semiconductor material, preparation method thereof and electroluminescent device - Google Patents
Organic semiconductor material, preparation method thereof and electroluminescent device Download PDFInfo
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- 0 CC(C)(C)c(cc1)cc(C23c4ccccc4N(c4ccccc4)c4c2cccc4)c1-c(cc1)c3cc1-c(c(*)c1)cc(C)c1-c1c(C)cc(C(C)(C)C)c(*)c1 Chemical compound CC(C)(C)c(cc1)cc(C23c4ccccc4N(c4ccccc4)c4c2cccc4)c1-c(cc1)c3cc1-c(c(*)c1)cc(C)c1-c1c(C)cc(C(C)(C)C)c(*)c1 0.000 description 7
- DNIJBWZQCXOWFP-SQFISAMPSA-N CC/C(/C(C(C)=C1)=CC(C)=CC1Br)=C(\C=C)/[S+]=O Chemical compound CC/C(/C(C(C)=C1)=CC(C)=CC1Br)=C(\C=C)/[S+]=O DNIJBWZQCXOWFP-SQFISAMPSA-N 0.000 description 1
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Abstract
The invention provides an organic semiconductor material. The organic semiconductor material has the chemical formula represented by a formula shown in specifications, wherein R is C1-C20 alkyl, and n is an integer between 10 and 100. The organic semiconductor material provided by the invention simultaneously has an excellent hole transport property and a relatively high triplet energy level, and the triplet energy level is higher than 2.75eV, so that energy is effectively prevented from being transferred back to a main body material during luminescence, and the luminescence efficiency is greatly increased. According to the organic semiconductor material, a relatively simple synthesis route is adopted, process flows are reduced, raw materials are cheap and are easily obtained, and the preparation cost is reduced.
Description
Technical field
The invention belongs to field of photovoltaic materials, be specifically related to a kind of organic semiconductor material, preparation method and electroluminescent device.
Background technology
Prepared with Alq by evaporation coating method from people's reported first such as Kodak C.W.Tang in 1987
3since bi-layer devices structure for luminescent material, organic electroluminescent just obtains the very big concern of people.Organic electroluminescent can be divided into fluorescence and phosphorescence electroluminescent.According to spin quantum statistical theory, the formation probability ratio of singlet excitons and triplet exciton is 1:3, and namely singlet excitons only accounts for 25% of " electron-hole pair ".Therefore, the fluorescence coming from the radiative transition of singlet excitons just only accounts for 25% of total input energy.
Organic electroluminescence device has that driving voltage is low, fast response time, angular field of view are wide and changes luminescent properties by chemical structure fine setting makes rich color, easily realize the advantages such as resolving power is high, lightweight, large-area flat-plate display, be described as " 21 century flat panel display ", become the focus of the subjects such as material, information, physics and flat pannel display area research.But, because the excited state exciton lifetime of transition metal complex is relatively long, cause unwanted triplet state-triplet state (T
1-T
1) cancellation in device real work.In order to overcome this problem, triplet emission thing is often doped in organic host material by investigators.
In recent years, green and red phosphorescent OLED shows gratifying electroluminescent efficiency.And blue phosphorescent device is little efficiently, simultaneously major cause lacks to have good carrier transmission performance and higher triplet (E
t) material of main part.
Summary of the invention
For solving the problem, the invention provides a kind of organic semiconductor material, this organic semiconductor material has excellent hole transport character and higher triplet simultaneously, triplet is greater than 2.75eV, effectively prevent energy in luminescence process from returning to material of main part, greatly improve luminous efficiency, organic semiconductor material of the present invention is that blue emitting phosphor material of main part provides new selectable kind.Present invention also offers the preparation method of this organic semiconductor material, and comprise the electroluminescent device of this organic semiconductor material.
On the one hand, the invention provides a kind of organic semiconductor material, the chemical formula of described organic semiconductor material is as follows:
wherein, R is C
1~ C
20alkyl, n is the integer of 10 ~ 100.
Second aspect, the invention provides a kind of preparation method of organic semiconductor material, comprises the steps:
Compd A is provided:
and compd B:
wherein, R is C
1~ C
20alkyl; Under an inert atmosphere, be in the organic solvent that is added into containing catalyzer and alkaline solution of 1:1 ~ 1:1.2 by compd A and compd B according to mol ratio, Suzuki coupling reaction is carried out 12 ~ 96 hours at 70 ~ 130 DEG C, described catalyzer is organic palladium or the mixture for organic palladium and organophosphor ligand, obtains the organic semiconductor material P that following structural formula represents:
wherein, n is the integer of 10 ~ 100.
Preferably, the preparation method of described organic semiconductor material also comprises the step of organic semiconductor material P being carried out separation and purification, described purification procedures is as follows: add methyl alcohol precipitating in the solution after carrying out Suzuki coupling reaction to described compd A and compd B and filter, extracting is carried out with methyl alcohol and normal hexane successively by filtering the solid obtained, by the solid chloroform after extracting, collect evaporating solvent after chloroformic solution obtain purifying after organic semiconductor material P.
Preferably, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
Preferably, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
Preferably, described organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, three (o-methoxyphenyl) phosphines or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
Preferably, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1:100.
The third aspect, the invention provides a kind of electroluminescent device, comprise the substrate with anode, luminescent layer and the cathode layer that stack gradually, described luminescent layer is the mixture of material of main part and guest materials, the organic semiconductor material that wherein material of main part is as follows:
wherein, R is C
1~ C
20alkyl, n is the integer of 10 ~ 100, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] closes iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
Preferably, the mass percent of described material of main part and described guest materials is 5% ~ 15%.
Preferably, anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
The invention provides a kind of organic semiconductor material, preparation method and electroluminescent device, there is following beneficial effect: there is excellent hole transport character and higher triplet simultaneously, triplet is greater than 2.75eV, effectively prevent energy in luminescence process from returning to material of main part, greatly improve luminous efficiency.This organic semiconductor material have employed better simply synthetic route, decreases technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device obtained for material of main part with organic semiconductor material obtained in embodiment 1;
Fig. 2 is the differential scanning calorimetric curve of organic semiconductor material obtained in embodiment 1.
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 monomer A commercially obtains, and monomers B commercially obtains.
The invention provides a kind of organic semiconductor material, the chemical formula of described organic semiconductor material is as follows:
wherein, R is C
1~ C
20alkyl, n is the integer of 10 ~ 100.
This organic semiconductor material has bipolarity carrier transport ability, makes the hole in luminescent layer and electric transmission balance; Have excellent hole transport character and higher triplet, triplet is greater than 2.75eV simultaneously, effectively prevents energy in luminescence process from returning to material of main part, greatly improves luminous efficiency.This organic semiconductor material have employed better simply synthetic route, decreases technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced, and therefore organic semiconductor material of the present invention has blue emitting phosphor material of main part.
The invention provides a kind of preparation method of organic semiconductor material, comprise the steps:
Compd A is provided:
and compd B:
wherein, R is C
1~ C
20alkyl; Under an inert atmosphere, be in the organic solvent that is added into containing catalyzer and alkaline solution of 1:1 ~ 1:1.2 by compd A and compd B according to mol ratio, Suzuki coupling reaction is carried out 12 ~ 96 hours at 70 ~ 130 DEG C, described catalyzer is organic palladium or the mixture for organic palladium and organophosphor ligand, obtains the organic semiconductor material P that following structural formula represents:
wherein, n is the integer of 10 ~ 100.
The preparation method of described organic semiconductor material further comprises the step of organic semiconductor material P being carried out separation and purification, described purification procedures is as follows: add methyl alcohol precipitating in the solution after carrying out Suzuki coupling reaction to described compd A and compd B and filter, extracting is carried out with methyl alcohol and normal hexane successively by filtering the solid obtained, by the solid chloroform after extracting, collect evaporating solvent after chloroformic solution obtain purifying after organic semiconductor material P.
In present embodiment, extracting uses apparatus,Soxhlet's to carry out.
In present embodiment, evaporating solvent after collection chloroformic solution is obtained 50 DEG C under vacuo ~ 70 DEG C dryings of the organic semiconductor material P after purifying 24 hours ~ 72 hours.
Described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
Described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
Described organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, three (o-methoxyphenyl) phosphines or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
The mol ratio of the organic palladium in described catalyzer and described compd A is 1:20 ~ 1:100.
Have employed better simply synthetic route, thus reduce technical process, starting material are cheap and easy to get, and manufacturing cost is reduced.
The invention provides a kind of electroluminescent device, comprise the substrate with anode, luminescent layer and the cathode layer that stack gradually, described luminescent layer is the mixture of material of main part and guest materials, the organic semiconductor material that wherein material of main part is as follows:
wherein, R is C
1~ C
20alkyl, n is the integer of 10 ~ 100, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] closes iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
The mass percent of described guest materials and described material of main part is 5% ~ 15%.
Described anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
Organic luminescent device based on this material launches blue light, and luminous efficiency is high.
Embodiment 1:
Present embodiment discloses poly-{ 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-dihexyl sulphur dibenzofuran } (organic semiconductor material P1) that structural formula is following:
The preparation process of above-mentioned organic semiconductor material P1 is as follows:
Under argon shield, by 10-phenyl-2', 7'-bis-tetramethyl ethylene ketone boric acid ester-10H-spiral shell [acridine-9,9'-fluorenes] (132mg, 0.2mmol), 3,7-bis-bromo-4,8-dihexyl sulphur dibenzofuran (108mg, 0.2mmol) add in the flask filling 10ml toluene solvant, after abundant dissolving, salt of wormwood (2mL, 2mol/L) solution is joined in flask, vacuumize deoxygenation and be filled with argon gas, then bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol) is added; Flask is heated to 100 DEG C and carries out Suzuki coupling reaction 48h.Stop polyreaction after cooling, drip in flask in 50ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is extremely colourless with chloroform, collect chloroformic solution and be spin-dried for obtain red powder, obtain this and gather { 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-dihexyl sulphur dibenzofuran } organic semiconductor material, the lower 50 DEG C of dry 24h of last vacuum.Productive rate is 87%.
The above-mentioned reaction formula preparing organic semiconductor material P1 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=33.6kDa, M
w/ M
n=2.3.
See the thermogravimetic analysis (TGA) that accompanying drawing 2 is organic semiconductor material prepared by the present embodiment, thermogravimetric curve (TGA) test completes in the measurement of Perkin-Elmer Series7 Thermo System, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 428 DEG C.
The uv-visible absorption spectra figure of the organic semiconductor material P1 of preparation in embodiment 1, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 700nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 568nm, and wide absorption spectrum shows that P1 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate the organic semiconductor material P1 triplet emission characteristic of preparation in embodiment 1.Under the liquid nitrogen of 77K, organic semiconductor material P1 shows very strong phosphorescent emissions, emission peak is at 447nm, corresponding triplet energy state is 2.77eV, be much higher than phosphor material two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as Blue-light emitting host material.
Adopt transition time (TOP) method to test the hole mobility of organic semiconductor material prepared by the present embodiment, test result is 2.9 × 10
-4cm
2/ Vs.
Embodiment 2:
Present embodiment discloses poly-{ 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-dimethyl sulphide dibenzofuran } (organic semiconductor material P2) that structural formula is following:
Under nitrogen and the protection of argon gas gas mixture; by 10-phenyl-2'; 7'-bis-tetramethyl ethylene ketone boric acid ester-10H-spiral shell [acridine-9; 9'-fluorenes] (198mg; 0.3mmol), 3; 7-bis-bromo-4; 8-dimethyl sulphide dibenzofuran (121mg; 0.3mmol) 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 tetra-triphenylphosphine palladium (4mg, 0.003mmol) is added wherein; sodium bicarbonate (3mL, 2mol/L) solution is added again after abundant dissolving.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 96h.Stop polyreaction after cooling, drip in flask in 40ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is extremely colourless with chloroform, collect chloroformic solution and be spin-dried for obtain red powder, gathered { 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-dimethyl sulphide dibenzofuran } organic semiconductor material, the lower 50 DEG C of dry 24h of last vacuum.Productive rate is 84%.
The above-mentioned reaction formula preparing organic semiconductor material P2 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=62.4kDa, M
w/ M
n=2.0.
The thermogravimetic analysis (TGA) of organic semiconductor material P2 prepared by the present embodiment 2, thermogravimetric curve (TGA) test completes in the measurement of Perkin-Elmer Series7 Thermo System, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 446 DEG C.
The uv-visible absorption spectra figure of the organic semiconductor material P2 of preparation in embodiment 2, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 700nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 567nm, and wide absorption spectrum shows that P2 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P2 triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P2 shows very strong phosphorescent emissions, emission peak is at 443nm, corresponding triplet energy state is 2.80eV, be much higher than phosphor material two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as Blue-light emitting host material.
Adopt transition time (TOP) method to test the hole mobility of organic semiconductor material prepared by the present embodiment, test result is 3.2 × 10
-4cm
2/ Vs.
Embodiment 3:
Present embodiment discloses poly-{ 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-bis-NSC 62789 base sulphur dibenzofuran } (organic semiconductor material P3) that structural formula is following:
Under nitrogen protection, by 10-phenyl-2', 7'-bis-tetramethyl ethylene ketone boric acid ester-10H-spiral shell [acridine-9,9'-fluorenes] (198mg, 0.3mmol), 3,7-bis-bromo-4,8-bis-NSC 62789 base sulphur dibenzofuran (309mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) joins the N filling 12mL, in the flask of dinethylformamide, salt of wormwood (3mL, 2mol/L) solution is added, after logical nitrogen purge gas is about 30min in flask subsequently after abundant dissolving; Flask is heated to 130 DEG C and carries out Suzuki coupling reaction 12h.Stopped reaction cool to room temperature, drip in 40ml methyl alcohol and carry out sedimentation in flask; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is extremely colourless with chloroform, collect chloroformic solution and be spin-dried for obtain red powder, gathered { 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-bis-NSC 62789 base sulphur dibenzofuran } organic semiconductor material, the lower 50 DEG C of dry 24h of last vacuum.Productive rate is 90%.
The above-mentioned reaction formula preparing organic semiconductor material P3 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=85.3kDa, M
w/ M
n=2.2.
The thermogravimetic analysis (TGA) of organic semiconductor material P3 prepared by the present embodiment 3, thermogravimetric curve (TGA) test completes in the measurement of Perkin-Elmer Series7 Thermo System, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 409 DEG C.
The uv-visible absorption spectra figure of the organic semiconductor material P3 of preparation in embodiment 3, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 566nm, and wide absorption spectrum shows that P3 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P3 triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P3 shows very strong phosphorescent emissions, emission peak is at 447nm, corresponding triplet energy state is 2.77V, be much higher than phosphor material two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as Blue-light emitting host material.
Adopt transition time (TOP) method to test the hole mobility of organic semiconductor material prepared by the present embodiment, test result is 2.1 × 10
-4cm
2/ Vs.
Embodiment 4:
Present embodiment discloses poly-{ 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-bis-normal butane base sulphur dibenzofuran } (organic semiconductor material P4) that structural formula is following:
Under nitrogen protection; by 10-phenyl-2'; 7'-bis-tetramethyl ethylene ketone boric acid ester-10H-spiral shell [acridine-9; 9'-fluorenes] (198mg; 0.3mmol), 3; 7-bis-bromo-4; 8-bis-normal butane base sulphur dibenzofuran (175mg; 0.36mmol), three or two argon benzyl acetones two palladium (9mg, 0.009mmol) and 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg; 0.072mmol) join the N filling 12mL; in the flask of dinethylformamide, after fully dissolving, add sodium carbonate (3mL, 2mol/L) solution.After in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 120 DEG C and carries out Suzuki coupling reaction 36h.Stop polyreaction after cooling, drip in flask in 40ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is extremely colourless with chloroform, collect chloroformic solution and be spin-dried for obtain red powder, gathered { 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-bis-normal butane base sulphur dibenzofuran } organic semiconductor material, the lower 50 DEG C of dry 24h of last vacuum.Productive rate is 82%.
The above-mentioned reaction formula preparing organic semiconductor material P4 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=12.8kDa, M
w/ M
n=2.5.
The thermogravimetic analysis (TGA) of organic semiconductor material P4 prepared by the present embodiment 4, thermogravimetric curve (TGA) test completes in the measurement of Perkin-Elmer Series7 Thermo System, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 435 DEG C.
The uv-visible absorption spectra figure of the organic semiconductor material P4 of preparation in embodiment 4, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 568nm, and wide absorption spectrum shows that P4 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P4 triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P4 shows very strong phosphorescent emissions, emission peak is at 445nm, corresponding triplet energy state is 2.79eV, be much higher than phosphor material two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as Blue-light emitting host material.
Adopt transition time (TOP) method to test the electronic mobility of organic semiconductor material prepared by the present embodiment, test result is 2.3 × 10
-4cm
2/ Vs.
Embodiment 5:
Present embodiment discloses poly-{ 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-bis-dodecyl sulphur dibenzofuran } (organic semiconductor material P5) that structural formula is following:
Under nitrogen protection; by 10-phenyl-2'; 7'-bis-tetramethyl ethylene ketone boric acid ester-10H-spiral shell [acridine-9,9'-fluorenes] (198mg, 0.3mmol), 3; 7-bis-bromo-4; 8-bis-dodecyl sulphur dibenzofuran (256mg, 0.36mmol), tetra-triphenylphosphine palladium (8mg, 0.006mmol) join and fill 15mL toluene and add in the twoport flask of 50mL; salt of wormwood (3mL, 2mol/L) solution is added after abundant dissolving.After in flask, logical nitrogen purge gas is about 20min subsequently; Flask is heated to 90 DEG C and carries out Suzuki coupling reaction 60h.Stop polyreaction after cooling, drip in flask in 40ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is extremely colourless with chloroform, collect chloroformic solution and be spin-dried for obtain red powder, gathered { 2,7-bis-base-9,9-bis-(triphenylamine base) fluorenes-co-3,7-bis-base-4,8-bis-dodecyl sulphur dibenzofuran } organic semiconductor material, the lower 50 DEG C of dry 24h of last vacuum.Productive rate is 78%.
The above-mentioned reaction formula preparing organic semiconductor material P5 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=102.6kDa, M
w/ M
n=2.0.
The thermogravimetic analysis (TGA) of organic semiconductor material P5 prepared by the present embodiment 5, thermogravimetric curve (TGA) test completes in the measurement of Perkin-Elmer Series7 Thermo System, and under nitrogen gas stream protection, heat-up rate is 10K/min.Thermal weight loss temperature (the T of 5%
d) be 417 DEG C.
The uv-visible absorption spectra figure of the organic semiconductor material P5 of preparation in embodiment 5, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers between 300nm ~ 800nm, have comparatively large wider absorption, wherein maximum absorption band is positioned at 565nm, and wide absorption spectrum shows that P5 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P5 triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P5 shows very strong phosphorescent emissions, emission peak is at 443nm, corresponding triplet energy state is 2.80eV, be much higher than phosphor material two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as blue emitting phosphor material of main part.
Adopt transition time (TOP) method to test the hole mobility of organic semiconductor material prepared by the present embodiment, test result is 1.9 × 10
-4cm
2/ Vs.
Application Example
Organic electroluminescence device 300, as Fig. 1, it comprises substrate 301 to its structure, anode 302, hole injection layer 303, luminescent layer 304, hole blocking layer 305, electron transfer layer 306, electron injection buffer layer 307, negative electrode 308.
The material of substrate 301 in the present embodiment is glass, vacuum plating anode 302 successively in substrate 301, hole injection layer 303, luminescent layer 304, hole blocking layer 305, electron transfer layer 306, electron injection buffer layer 307, negative electrode 308, anode 302 adopts square resistance to be the tin indium oxide of 10 ~ 20 Ω/, thickness is 150nm, hole injection layer 303 adopts poly-(3, 4-ethene dioxythiophene)-polystyrolsulfon acid, thickness is 30nm, the compound poly-{ 2 that luminescent layer 304 main body luminescent material adopts the invention process 1 to prepare, 7-bis-base-9, 9-bis-(triphenylamine base) fluorenes-co-3, 7-bis-base-4, 8-dihexyl sulphur dibenzofuran }, and to take material of main part as benchmark doping mass percent be 13% guest emitting material two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (III), luminescent layer 305 thickness is 20nm, hole blocking layer 305 adopts 2, 9-dimethyl-4, 7-phenylbenzene-1, 10-phenanthroline, thickness is 30nm, electron transfer layer 306 adopts three-oxine aluminium, thickness is 30nm, electron injection buffer layer 307 adopts lithium fluoride, thickness is 1.5nm, negative electrode 308 adopts metallic aluminium, thickness is 150nm.
Organic layer and metal level all adopt thermal evaporation process to deposit, and vacuum tightness is 10
-3~ 10
-5pa, the thickness of film adopts film thickness monitoring instrument to monitor, except guest materials, the vaporator rate of all organic materialss is
second, the vaporator rate of lithium fluoride is
second, the vaporator rate of metallic aluminium is
second.
Current versus brightness-the voltage characteristic of this device completes by with Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) correcting silicon photoelectric diode, electroluminescent spectrum is by French JY company SPEX CCD3000 spectrometer measurement, and all measurements all complete in atmosphere at room temperature.The maximum lumen efficiency of device is 7.7cd/A, and high-high brightness is 21520cd/m
2.
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 semiconductor material, is characterized in that, the chemical formula of described organic semiconductor material is as follows:
wherein, R is C
1~ C
20alkyl, n is the integer of 10 ~ 100.
2. a preparation method for organic semiconductor material, is characterized in that, comprises the steps:
Compd A is provided:
and compd B:
wherein, R is C
1~ C
20alkyl; Under an inert atmosphere, be in the organic solvent that is added into containing catalyzer and alkaline solution of 1:1 ~ 1:1.2 by compd A and compd B according to mol ratio, Suzuki coupling reaction is carried out 12 ~ 96 hours at 70 ~ 130 DEG C, described catalyzer is organic palladium or the mixture for organic palladium and organophosphor ligand, obtains the organic semiconductor material P that following structural formula represents:
wherein, n is the integer of 10 ~ 100.
3. preparation method as claimed in claim 2, it is characterized in that, also comprise the step of organic semiconductor material P being carried out separation and purification, described purification procedures is as follows: add methyl alcohol precipitating in the solution after carrying out Suzuki coupling reaction to described compd A and compd B and filter, extracting is carried out with methyl alcohol and normal hexane successively by filtering the solid obtained, by the solid chloroform after extracting, collect evaporating solvent after chloroformic solution obtain purifying after organic semiconductor material P.
4. preparation method as claimed in claim 2, it is characterized in that, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
5. preparation method as claimed in 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 solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
6. preparation method as claimed in claim 2, it is characterized in that, described organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, three (o-methoxyphenyl) phosphines or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
7. preparation method as claimed in claim 2, it is characterized in that, the mol ratio of the organic palladium in described catalyzer and described compd A is 1:20 ~ 1:100.
8. an electroluminescent device, is characterized in that, comprises the substrate with anode, luminescent layer and the cathode layer that stack gradually, and described luminescent layer is the mixture of material of main part and guest materials, the organic semiconductor material that wherein material of main part is as follows:
wherein, R is C
1~ C
20alkyl, n is the integer of 10 ~ 100, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] closes iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
9. electroluminescent device as claimed in claim 8, it is characterized in that, the mass percent of described material of main part and described guest materials is 5% ~ 15%.
10. electroluminescent device as claimed in claim 8, it is characterized in that, described anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942799A (en) * | 2019-03-21 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of conjugated polymer of siliceous spiro fluorene acridine unit and preparation method thereof, organic electroluminescence device |
| CN111205278A (en) * | 2020-03-03 | 2020-05-29 | 苏州大学 | Spirofluorene triphenylamine derivative and application thereof in organic electroluminescent device |
-
2013
- 2013-09-24 CN CN201310438606.9A patent/CN104448248A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942799A (en) * | 2019-03-21 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of conjugated polymer of siliceous spiro fluorene acridine unit and preparation method thereof, organic electroluminescence device |
| CN109942799B (en) * | 2019-03-21 | 2022-06-07 | 中国科学院长春应用化学研究所 | Conjugated polymer containing silicon spirofluorene acridine unit, preparation method thereof and organic electroluminescent device |
| CN111205278A (en) * | 2020-03-03 | 2020-05-29 | 苏州大学 | Spirofluorene triphenylamine derivative and application thereof in organic electroluminescent device |
| CN111205278B (en) * | 2020-03-03 | 2021-11-16 | 苏州大学 | Spirofluorene triphenylamine derivative and application thereof in organic electroluminescent device |
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