CN103965439A - Organic semiconductor material, preparation method and electroluminescent device - Google Patents

Organic semiconductor material, preparation method and electroluminescent device Download PDF

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CN103965439A
CN103965439A CN201310038744.8A CN201310038744A CN103965439A CN 103965439 A CN103965439 A CN 103965439A CN 201310038744 A CN201310038744 A CN 201310038744A CN 103965439 A CN103965439 A CN 103965439A
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semiconductor material
organic semiconductor
compd
organic
preparation
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周明杰
王平
张振华
黄辉
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The present invention provides an organic semiconductor material having the following chemical formula, wherein R is C1-C20 alkyl, and n is an integer of 10-100. According to the present invention, the hole transporting property of the organic semiconductor material is 10<-4> cm<2>/(V.s) magnitude order, and the organic semiconductor material has a high triplet energy level of greater than 2.8 eV, such that the condition that energy is returned to the main body material during the luminescence process can be effectively prevented so as to substantially increase the luminescence efficiency; the organic semiconductor material can be used as the blue light phosphorescent main body material; and the organic semiconductor material preparation method adopts the simple synthesis route, and has characteristics of process reducing, easily available raw materials and manufacturing cost reducing.

Description

A kind of organic semiconductor material, preparation method and electroluminescent device
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
Organic electroluminescence device has that driving voltage is low, fast response time, angular field of view are wide and can be finely tuned and be changed luminescent properties and make rich color by chemical structure, easily realize the advantages such as resolving power is high, lightweight, large-area flat-plate demonstration, 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.Following commercialization Organic Light Emitting Diode efficiently will contain organo-metallic phosphorescent substance possibly, because they can all catch singlet and triplet excitons, thereby realize 100% internal quantum efficiency.But, because the excited state exciton life-span 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, investigators are often doped to triplet state shiner in organic main body material.
In recent years, green and red phosphorescent OLED device exhibits goes out gratifying electroluminescent efficiency.And blue phosphorescent device is little efficiently, major cause is to lack to have good carrier transmission performance and higher triplet (E simultaneously t) material of main part.
Summary of the invention
For addressing the above problem, the invention provides a kind of organic semiconductor material, the hole transport performance of this organic semiconductor material is 10 -4cm 2/ (Vs) order of magnitude, also there is higher triplet, triplet is greater than 2.8eV, effectively prevent that in luminescence process, energy returns to material of main part, greatly improve luminous efficiency, organic semiconductor material of the present invention provides new selectable kind for blue emitting phosphor material of main part.The present invention also provides the preparation method of this organic semiconductor material, and the electroluminescent device that comprises 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, the integer that n is 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 inert atmosphere, be within 1: 1 ~ 1: 1.2, to be added in the organic solvent that contains catalyzer and alkaline solution compd A and compd B according to mol ratio, at 70～130 DEG C, carry out Suzuki coupling reaction 12～96 hours, 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, the integer that n is 10 ~ 100.
Preferably, the preparation method of described organic semiconductor material also comprises the step of organic semiconductor material P being carried out to separation and purification, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the organic semiconductor material P after purifying.
Preferably, described organic solvent is selected from least one in toluene, DMF, 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 bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine 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 mol ratio of the organic palladium in described catalyzer and described compd A is 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, wherein material of main part organic semiconductor material as follows: wherein, R is C 1~ C 20alkyl, n is 10 ~ 100 integer, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes that iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] close 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: the hole transport performance that the invention provides organic semiconductor material is 10 -4cm 2/ (Vs) order of magnitude, also have higher triplet, triplet is greater than 2.8eV, effectively prevents that in luminescence process, energy returns to material of main part, greatly improve luminous efficiency, this organic semiconductor material can be used as blue emitting phosphor material of main part.This material has adopted better simply synthetic route, has reduced technical process, and starting material are cheap and easy to get,
Manufacturing cost is reduced.
Brief description of the drawings
The structural representation of Fig. 1 organic electroluminescence device that to be organic semiconductor material to make in embodiment 1 make as material of main part;
Fig. 2 is the thermogravimetic analysis (TGA) figure of the organic semiconductor material that makes in embodiment 1.
Embodiment
In order to understand better the content of patent of the present invention, further illustrate technology case of the present invention 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 is bought and is obtained from the market, and monomers B is bought and obtained from the market.
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, the integer that n is 10 ~ 100.
The hole transport performance of this organic semiconductor material is 10 -4cm 2/ (Vs) order of magnitude, also have higher triplet, triplet is greater than 2.8eV, effectively prevents that in luminescence process, energy returns to material of main part, greatly improve luminous efficiency, this organic semiconductor material can be used as blue emitting phosphor material of main part.
The preparation method who the invention provides a kind of organic semiconductor material, comprises the steps:
Compd A is provided: and compd B: wherein, R is C 1~ C 20alkyl; Under inert atmosphere, be that 1: 1 ~ 1:1.2 is added in the organic solvent that contains catalyzer and alkaline solution by compd A and compd B according to mol ratio, at 70～130 DEG C, carry out Suzuki coupling reaction 12～96 hours, 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, the integer that n is 10 ~ 100.
In specific embodiment, the preparation method of described organic semiconductor material further comprises the step of organic semiconductor material P being carried out to separation and purification, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the organic semiconductor material P after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, by collect evaporating solvent after chloroformic solution obtain organic semiconductor material P after purifying under vacuum 50 DEG C～70 DEG C dry 24 hours～48 hours.
In specific embodiment, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
In specific embodiment, 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.
In specific embodiment, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
In specific embodiment, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1:100.
Adopted better simply synthetic route, thereby reduced 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, wherein material of main part organic semiconductor material as follows: wherein, R is C 1~ C 20alkyl, n is 10 ~ 100 integer, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes that iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] close iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
In specific embodiment, the mass percent of described guest materials and described material of main part is 5%～15%.
In specific embodiment, anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
Organic luminescent device transmitting blue light based on this material, and luminous efficiency is high.
Embodiment 1:
The present embodiment discloses structural formula following poly-{ 2,7-, bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-normal hexane base-2,7-bis-base fluorenes } (organic semiconductor material P1):
The preparation process of above-mentioned organic semiconductor material P1 is as follows:
Under argon shield, by 2,7-bis-tetramethyl ethylene ketone boric acid ester-9-[4-(N, N-bis-phenylaminos) phenyl]-9-phenyl fluorenes (148mg, 0.2mmol), 9,9-bis-normal hexane base-2,7-dibromo fluorenes (98mg, 0.2mmol) add in the flask that fills 10ml toluene solvant, after fully dissolving, salt of wormwood (2mL, 2mol/L) solution is joined in flask, vacuumize deoxygenation and be filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 DEG C and carries out Suzuki coupling reaction 48h.After cooling, stop polyreaction, in 50ml methyl alcohol, carry out sedimentation to dripping in flask; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then taking chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, obtain this poly-{ 2,7-bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-normal hexane base-2,7-bis-base fluorenes } organic semiconductor material, the last lower 50 DEG C of dry 24h of vacuum.Productive rate is 85%.
The above-mentioned reaction formula of preparing organic semiconductor material P1 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=54.2kDa, M w/ M n=2.2.
Are thermogravimetic analysis (TGA) figure of the organic semiconductor material prepared of the present embodiment referring to accompanying drawing 2, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 443 DEG C as seen from the figure.
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: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 574nm.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate the organic semiconductor material P1 triplet state 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 441nm, corresponding triplet energy state is 2.81eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl 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.
Taking ITO/PEDOT:PSS/ the present embodiment 1 organic semiconductor material P1/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material P1 that hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and the hole mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the hole mobility that obtains organic semiconductor material P1 is 1.6 × 10 -4cm 2/ Vs.
Embodiment 2:
The present embodiment discloses structural formula following poly-{ 2,7-, bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-diformazan alkyl-2,7-bis-base fluorenes } (organic semiconductor material P2):
Under nitrogen and the protection of argon gas gas mixture; by 2; 7-bis-tetramethyl ethylene ketone boric acid ester-9-[4-(N; N-bis-phenylaminos) phenyl]-9-phenyl fluorenes (221mg; 0.3mmol), 9; 9-diformazan alkyl-2; 7-dibromo fluorenes (129mg; 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF); after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then tetra-triphenylphosphine palladium (4mg, 0.003mmol) is added wherein; after fully dissolving, add again sodium bicarbonate (3mL, 2mol/L) solution.After the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 DEG C and carry out Suzuki coupling reaction 96h again.After cooling, stop polyreaction, in 40ml methyl alcohol, carry out sedimentation to dripping in flask; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then taking chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, gathered { 2,7-bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-diformazan alkyl-2,7-bis-base fluorenes } organic semiconductor material, the last lower 50 DEG C of dry 24h of vacuum.Productive rate is 76%.
The above-mentioned reaction formula of preparing organic semiconductor material P2 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=37.5kDa, M w/ M n=2.1.
The thermogravimetic analysis (TGA) figure of organic semiconductor material P2 prepared by the present embodiment 2, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 462 DEG C as seen from the figure.
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: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 570nm.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P2 triplet state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P2 shows very strong phosphorescent emissions, emission peak is at 440nm, corresponding triplet energy state is 2.82eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl 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.
Taking ITO/PEDOT:PSS/ the present embodiment 2 organic semiconductor material P2/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material P2 that hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and the hole mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the hole mobility that obtains organic semiconductor material P2/ is 1.7 × 10 -4cm 2/ Vs.
Embodiment 3:
The present embodiment discloses structural formula following poly-{ 2,7-, bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-NSC 62789 base-2,7-bis-base fluorenes } (organic semiconductor material P3):
Under nitrogen protection, by 2,7-bis-tetramethyl ethylene ketone boric acid ester-9-[4-(N, N-bis-phenylaminos) phenyl]-9-phenyl fluorenes (221mg, 0.3mmol), 9,9-bis-NSC 62789 base-2,7-dibromo fluorenes (292mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) joins the N that fills 12mL, in the flask of dinethylformamide, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution, in flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 130 DEG C and carries out Suzuki coupling reaction 12h.Stopped reaction cool to room temperature, carry out sedimentation to dripping in flask in 40ml methyl alcohol; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then taking chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, gathered { 2,7-bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-NSC 62789 base-2,7-bis-base fluorenes } organic semiconductor material, the last lower 50 DEG C of dry 24h of vacuum.Productive rate is 78%.
The above-mentioned reaction formula of preparing organic semiconductor material P3 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=41.5kDa, M w/ M n=2.2.
The thermogravimetic analysis (TGA) figure of organic semiconductor material P3 prepared by the present embodiment 3, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 425 DEG C as seen from the figure.
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: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 576nm, 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 state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P3 shows very strong phosphorescent emissions, emission peak is at 441nm, corresponding triplet energy state is 2.81eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl 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.
Taking ITO/PEDOT:PSS/ the present embodiment 3 organic semiconductor material P3/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material P3 that hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and the hole mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the hole mobility that obtains organic semiconductor material P3 is 1.2 × 10 -4cm 2/ Vs.
Embodiment 4:
The present embodiment discloses structural formula following poly-{ 2,7-, bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-normal butane base-2,7-bis-base fluorenes } (organic semiconductor material P4):
Under nitrogen protection; by 2; 7-bis-tetramethyl ethylene ketone boric acid ester-9-[4-(N; N-bis-phenylaminos) phenyl]-9-phenyl fluorenes (221mg; 0.3mmol), 9; 9-bis-normal butane base-2; 7-dibromo fluorenes (157mg; 0.36mmol)), three or two argon benzyl acetone two palladiums (9mg, 0.009mmol) and 2-dicyclohexyl phosphines-2 ', 6 '-dimethoxy-biphenyl (29mg; 0.072mmol) join the N that fills 12mL; in the flask of dinethylformamide, after fully dissolving, add sodium carbonate (3mL, 2mol/L) solution.In flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 120 DEG C and carries out Suzuki coupling reaction 36h.After cooling, stop polyreaction, in 40ml methyl alcohol, carry out sedimentation to dripping in flask; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then taking chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, gathered { 2,7-bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-normal butane base-2,7-bis-base fluorenes } organic semiconductor material, the last lower 50 DEG C of dry 24h of vacuum.Productive rate is 75%.
The above-mentioned reaction formula of preparing organic semiconductor material P4 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=16.6kDa, M w/ M n=2.4.
The thermogravimetic analysis (TGA) figure of organic semiconductor material prepared by the present embodiment 4, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 450 DEG C as seen from the figure.
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: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 573nm, 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 state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P4 shows very strong phosphorescent emissions, emission peak is at 440nm, corresponding triplet energy state is 2.82eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl 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.
Taking ITO/PEDOT:PSS/ the present embodiment 4 organic semiconductor material P4/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material P4 that hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and the hole mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the hole mobility that obtains organic semiconductor material P4 is 1.4 × 10 -4cm 2/ Vs.
Embodiment 5:
The present embodiment discloses structural formula following poly-{ 2,7-, bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-dodecyl-2,7-bis-base fluorenes } (organic semiconductor material P5):
Under nitrogen protection; by 2; 7-bis-tetramethyl ethylene ketone boric acid ester-9-[4-(N, N-bis-phenylaminos) phenyl]-9-phenyl fluorenes (221mg, 0.3mmol), 9; 9-bis-dodecyl-2; 7-dibromo fluorenes (238mg, 0.36mmol), tetra-triphenylphosphine palladium (8mg, 0.006mmol) join and fill in the twoport flask that 15mL toluene adds 50mL; after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution.In flask, lead to after the about 10min of nitrogen purge gas subsequently; Flask is heated to 90 DEG C and carries out Suzuki coupling reaction 60h.After cooling, stop polyreaction, in 40ml methyl alcohol, carry out sedimentation to dripping in flask; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then taking chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, gathered { 2,7-bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9,9-bis-dodecyl-2,7-bis-base fluorenes } organic semiconductor material, the last lower 50 DEG C of dry 24h of vacuum.Productive rate is 87%.
The above-mentioned reaction formula of preparing organic semiconductor material P5 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M n=83.6kDa, M w/ M n=2.0.
The thermogravimetic analysis (TGA) figure of organic semiconductor material P5 prepared by the present embodiment 5, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 438 DEG C as seen from the figure.
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: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 575nm, 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 state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P5 shows very strong phosphorescent emissions, emission peak is at 438nm, corresponding triplet energy state is 2.83eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl 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.
Taking ITO/PEDOT:PSS/ the present embodiment 5 organic semiconductor material P5/Au as device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the organic semiconductor material P5 that hole transmission layer adopts the present embodiment to prepare, negative electrode adopts metallic aluminium, and the hole mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the hole mobility that obtains organic semiconductor material P5 is 1.5 × 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, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronic injection buffer layer 307, negative electrode 308.
In the present embodiment, the material of substrate 301 is glass, vacuum plating anode 302 successively in substrate 301, hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronic injection buffer layer 307, negative electrode 308, it is the tin indium oxide of 10 ~ 20 Ω/ that anode 302 adopts square resistance, thickness is 150nm, hole injection layer 303 adopts poly-(3, 4-ethene dioxythiophene)-polystyrolsulfon acid, thickness is 30nm, hole transmission layer 304 adopts N, N '-phenylbenzene-N, N '-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines, thickness is 20nm, prepared by luminescent layer 305 main body luminescent materials employing the invention process 1 gathers { 2, 7-bis-bases-9-(2 '-Ji-9 '-phenyl carbazole)-9-phenyl fluorenes-co-9, 9-bis-normal hexane base-2, 7-bis-base fluorenes }, and taking material of main part as benchmark the object luminescent material two (4 of doping mass percent as 10%, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (III), luminescent layer 305 thickness are 20nm, electron transfer layer 306 adopts 5 (4, 7-phenylbenzene-1, 10-phenanthroline, thickness is 30nm, electronic 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 deposits to complete, and vacuum tightness is 10 -3pa～10 -5pa, the thickness of film adopts film thickness monitoring instrument to monitor, and except guest materials, the vaporator rate of all organic materialss is the vaporator rate of lithium fluoride is the vaporator rate of metallic aluminium is
This electroluminescent device has higher luminous efficiency, can be widely used in the luminous field such as blueness or white.Electric current-the brightness-voltage characteristic of device is that all measurements that completed by the Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) with correction silicon photoelectric diode all complete in atmosphere at room temperature.Result shows: the maximum electrical efficiency of device is 9.6cd/A, and high-high brightness is 24150cd/m 2.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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, the integer that n is 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 inert atmosphere, be within 1: 1 ~ 1: 1.2, to be added in the organic solvent that contains catalyzer and alkaline solution compd A and compd B according to mol ratio, at 70～130 DEG C, carry out Suzuki coupling reaction 12～96 hours, 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, the integer that n is 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 to separation and purification, described purification procedures is as follows: carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction to described compd A and compd B, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the organic semiconductor material P after purifying.
4. preparation method as claimed in claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
5. preparation method as claimed in claim 2, 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 bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine 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, is characterized in that, the organic palladium in described catalyzer and the mol ratio of described compd A are 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, wherein material of main part organic semiconductor material as follows:
wherein, R is C 1~ C 20alkyl, n is 10 ~ 100 integer, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes that iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] close iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
9. electroluminescent device as claimed in claim 8, 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, 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.
CN201310038744.8A 2013-01-31 2013-01-31 Organic semiconductor material, preparation method and electroluminescent device Pending CN103965439A (en)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JAE-KYU JIN ET AL.: "Synthesis and Device Performance of a Highly Efficient Fluorene-Based Blue Emission Polymer Containing Bulky 9,9-Dialkylfluorene Substituents", 《MACROMOLECULES》 *
RIGOBERTO C. ADVINCULA ET AL.: "《Thin Films: Preparation, Characterization, Applications》", 31 December 2002, SPRINGER US *

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Application publication date: 20140806