CN102653546A - Bipolar blue-light main material and preparation method thereof and organic electroluminescent device - Google Patents

Bipolar blue-light main material and preparation method thereof and organic electroluminescent device Download PDF

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CN102653546A
CN102653546A CN2011100485140A CN201110048514A CN102653546A CN 102653546 A CN102653546 A CN 102653546A CN 2011100485140 A CN2011100485140 A CN 2011100485140A CN 201110048514 A CN201110048514 A CN 201110048514A CN 102653546 A CN102653546 A CN 102653546A
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phenyl carbazole
fluorene derivatives
dibromo
main part
layer
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CN102653546B (en
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周明杰
王平
张振华
张娟娟
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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 invention belongs to the field of photoelectron materials, and discloses a bipolar blue-light main material, a preparation method and an application thereof; the material has the following general formula, wherein R is H or a C1-C12 alkyl. The bipolar blue-light main material of the invention has good electron injection, hole-blocking and exciton-blocking capabilities, a high triplet-state energy level (ET), and excellent thermal stability.

Description

Bipolarity blue light material of main part and preparation method thereof and organic electroluminescence device
Technical field
The present invention relates to a kind of multipolymer, relate to a kind of bipolarity blue light material of main part that is used for the semiconductor material aspect and preparation method thereof more specifically.
The invention still further relates to the organic electroluminescence device of a kind of Application of bipolar blue light material of main part as luminescent layer.
Background technology
Organic electroluminescence device has that driving voltage is low, response speed is fast, angular field of view is wide and can change luminescent properties through the chemical structure fine setting make rich color; Realize advantages such as resolving power is high, in light weight, large-area flat-plate demonstration easily; Be described as " 21 century flat panel display ", become the focus of subjects such as material, information, physics and FPD area research.The commercialization Organic Light Emitting Diode will contain the organo-metallic phosphorescent substance possibly efficiently in future, because they can all catch singlet and triplet excitons, thereby realize 100% internal quantum efficiency.Yet,, cause unwanted triplet-triplet (T because the excited state exciton life-span of transition metal complex is long relatively 1-T 1) cancellation in the device real work.In order to overcome this problem, investigators often are doped to the triplet shiner in the organic main body material.A kind of ideal material of main part must satisfy following requirement: (i) triplet (E of material of main part T) greater than the triplet of object, purpose is in order to prevent that energy from turning back to main body again from object; (ii) have good carrier transmission performance, like this can the balancing charge flux and reduce driving voltage; (iii) have good thermostability and morphological stability, can prolong the working life of device like this.In recent years, green and red phosphorescent OLED device exhibits goes out gratifying electroluminescent efficiency.And efficiently the blue phosphorescent device seldom, major cause is to lack to have charge transport properties and higher triplet (E preferably simultaneously T) material of main part.
Summary of the invention
The object of the present invention is to provide a kind of bipolarity blue light material of main part, be used to address the above problem.
A kind of bipolarity blue light material of main part of the present invention has following general formula:
In the formula, R is H or C 1～C 12Alkyl; Preferred R is C 1～C 12The straight or branched alkyl.
Above-mentioned bipolarity blue light material of main part, its preparation scheme is following:
Step S1, provide structural formula to do
Figure BDA0000048394000000022
2,7-dibromo fluorenone and structural formula do
Figure BDA0000048394000000023
N-phenyl carbazole verivate; In the formula, R is H or C 1～C 12Alkyl;
Step S2, in oxygen-free environment; With mol ratio be 1: 14: 12; 7-dibromo fluorenone, N-phenyl carbazole and methylsulphonic acid place reactor drum to carry out building-up reactions; Make structural formula for
Figure BDA0000048394000000024
9; 9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorene derivatives;
In step S3, the oxygen-free environment, with make among the step S2 9,9-two [3 '-(N-phenyl carbazole base)]-2; 7-dibromo fluorene derivatives be dissolved in organic solvent (as; THF, ether) in, in solution, drip n-Butyl Lithium subsequently, add diphenyl phosphine chloride (PPh behind the stirring reaction again 2Cl, down with) proceed reaction after, make structural formula and do
Figure BDA0000048394000000031
Said bipolarity blue light material of main part, promptly 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives; Wherein, n-Butyl Lithium, 9,9-two [3 '-(N-phenyl carbazole base)]-2, the mol ratio of 7-dibromo fluorene derivatives, diphenyl phosphine chloride is 2.5: 1: 2.5;
The invention still further relates to a kind of organic electroluminescence device, this organic electroluminescence device is a laminate structure, and this laminate structure setting is followed successively by matrix, conductive layer, hole injection layer, hole transmission layer, luminescent layer, hole barrier-electron transfer layer and metal level; Wherein, luminescent layer employing structural formula is the bipolarity blue light material of main part of
Figure BDA0000048394000000032
.
The beneficial effect that bipolarity blue light material of main part provided by the invention has is: this compounds has good electronics injection and hole barrier and exciton blocking capability, higher triplet (ET) and good thermal stability.
Description of drawings
Fig. 1 is of the present invention 2,7-two (diphenyl phosphine oxygen base)-9, the thermogravimetic analysis (TGA) figure of 9-two [3 '-(N-phenyl carbazole base)] fluorenes;
Fig. 2 is of the present invention 2,7-two (diphenyl phosphine oxygen base)-9, and the blue phosphorescent material of main part of 9-two [3 '-(N-phenyl carbazole base)] fluorenes is the structural representation of the organic electroluminescence device of luminescent layer.
Embodiment
A kind of bipolarity blue light material of main part provided by the invention has following general formula:
Figure BDA0000048394000000041
In the formula, R is H or C 1～C 12Alkyl; Preferred R is C 1～C 12The straight or branched alkyl, the thermal weight loss of this bipolarity blue light material of main part is as shown in Figure 1.
The preparation scheme of above-mentioned a kind of bipolarity blue light material of main part is following:
Step S1, provide structural formula to do
Figure BDA0000048394000000042
2,7-dibromo fluorenone and structural formula do
Figure BDA0000048394000000043
N-phenyl carbazole verivate; In the formula, R is H or C 1～C 12Alkyl, preferred R is C 0～C 12The straight or branched alkyl;
Step S2: in the oxygen-free environment (constitute, like nitrogen, argon gas etc.) by rare gas element, with mol ratio be 1: 14: 12,7-dibromo fluorenone, N-phenyl carbazole and methylsulphonic acid (CH 3SO 3H) place reactor drum, to room temperature, make structural formula and do in 140 ℃ of following stirring reaction 6h postcooling
Figure BDA0000048394000000044
9,9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorene derivatives; Reaction formula is following:
Step S3: with make among the step S2 9; 9-two [3 '-(N-phenyl carbazole base)]-2; 7-dibromo fluorene derivatives is dissolved in the organic solvent, in solution, drips n-Butyl Lithium (n-BuLi) subsequently, behind-78 ℃ of following stirring reaction 1～5h, adds diphenyl phosphine chloride (PPh again 2Cl, down with) and be warming up to after room temperature proceeds to react 3～12h, make structural formula and do
Figure BDA0000048394000000052
Said bipolarity blue light material of main part (promptly 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives); Wherein, n-Butyl Lithium, 9,9-two [3 '-(N-phenyl carbazole base)]-2, the mol ratio of 7-dibromo fluorene derivatives, diphenyl phosphine chloride is 2.5: 1: 2.5, organic solvent is a kind of in THF, the ether; Reaction formula is following:
Figure BDA0000048394000000053
Among above-mentioned preparing method's step S2, question response is accomplished and is made 9,9-two [3 '-(N-phenyl carbazole base)]-2; Behind the 7-dibromo fluorene derivatives; Obtain this moment is to contain 9,9-two [3 '-(N-phenyl carbazole base)]-2, the mixing solutions of 7-dibromo fluorene derivatives; Need it is carried out purification process, treating processes is following:
S21, earlier with dichloromethane extraction 9,9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorene derivatives is washed with saturated sodium bicarbonate solution and distillation respectively again, concentrated organic layer obtains the blue solid crude product;
After S22, blue solid crude product adopt sherwood oil/methylene dichloride (mol ratio is 3: 1) to separate purification as leacheate through silica gel column chromatography; Obtain white solid product with acetone recrystallization again, promptly 9,9-two [3 '-(N-phenyl carbazole base)]-2; 7-dibromo fluorene derivatives, productive rate is about 75%.
Among above-mentioned preparing method's step S3, question response is accomplished and is made 2,7-two (diphenyl phosphine oxygen base)-9; 9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives, promptly behind the bipolarity blue light material of main part, obtain this moment is to contain 2; 7-two (diphenyl phosphine oxygen base)-9; The mixing solutions of 9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives needs it is carried out purification process, and treating processes is following:
S31, with 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives spends the night, ethyl acetate extraction is adopted in then water cancellation reaction, concentrates organic layer, use anhydrous magnesium sulfate drying, arrive solid crude product;
S32, solid crude product adopt sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtain white solid product;
S33, dissolve white solid product with methylene dichloride, add 30% ydrogen peroxide 50, stirring reaction spends the night under the room temperature; Separate organic layer, respectively with saturated aqueous common salt and distillation washing; Revolve the steaming solvent, obtain white solid and adopt ethyl acetate/methanol to separate to purify through silica gel column chromatography to obtain white pure solid product as leacheate, promptly 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives, productive rate is 30%.
Organic electroluminescence device of the present invention, this organic electroluminescence device are laminate structure, and this laminate structure setting is followed successively by matrix, conductive layer, hole injection layer, hole transmission layer, luminescent layer, hole barrier-electron transfer layer and Mg/Ag metal level; Wherein, It is the bipolarity blue light material of main part of that luminescent layer adopts structural formula; Promptly 2; 7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives.
Based on this; The present invention adopts 9, and 9-two [3 '-(N-phenyl carbazole base)] fluorenes is nuclear, and carbazyl has good hole transport ability; Diphenyl phosphine oxygen base is two arms; Diphenyl phosphine oxygen base has good electronic transmission performance, and synthetic one type of new bipolar material of main part is in the hope of preparing blue phosphorescent organic electroluminescent device efficiently.
Below in conjunction with accompanying drawing, further explain is done in preferred embodiment of the present invention.
Embodiment 1
Present embodiment disclose structural formula following 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorenes (R is H):
The preparation of above-mentioned target molecule is following:
One, 9,9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorenes
Figure BDA0000048394000000072
Under the argon shield, in the there-necked flask of 100mL, add 2 respectively, and the 7-dibromo fluorenone (3.303g, 9mmol), the N-phenyl carbazole (30.6g, 126mmol), methylsulphonic acid (0.9g, 9mmol).At 140 ℃ of following stirring reaction 6h, stopped reaction also is cooled to room temperature, uses dichloromethane extraction, more respectively with saturated sodium bicarbonate solution and distillation washing.Concentrate organic layer, obtain blue solid.Crude product obtains white solid product with acetone recrystallization after adopting sherwood oil/methylene dichloride (3: 1) to separate purification as leacheate through silica gel column chromatography again.Productive rate 75%.
1H-NMR(500MHz，CDCl 3)：7.21(m，2H)，7.32(m，4H)，7.39(d，4H)，7.45(m，2H)，7.53(d，2H)，7.55-7.60(m，8H)，7.65(d，4H)，7.96(s，2H)，8.0(d，2H).
Two, 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorenes
Figure BDA0000048394000000081
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, and (1.7mL 4.3mmol) is added drop-wise to 9 with n-Butyl Lithium (2.5M in hexane); 9-two [3 '-(N-phenyl carbazole base)]-2, (1.61g is in THF 2mmol) (100mL) solution for 7-dibromo fluorenes; Stir 3h down at-78 ℃, (0.8mL 4.3mmol) injects wherein rapidly through syringe with diphenyl phosphine chloride again; Obtain transparent pale yellow solution, be warming up to room temperature naturally after stirring reaction spend the night.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, uses anhydrous magnesium sulfate drying, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.With methylene dichloride (70mL) dissolving, add 30% ydrogen peroxide 50 (8mL), stirring reaction spends the night under the room temperature.Separate organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, obtain white solid and adopt ethyl acetate/methanol to obtain white solid product through silica gel column chromatography separation purification as leacheate; Productive rate is 30%.
1H-NMR(500MHz，CDCl 3)：7.16-7.21(m，6H)，7.29-7.32(m，8H)，7.38-7.41(m，8H)，7.45(m，2H)，7.55(m，4H)，7.59-7.62(m，12H)，7.76-7.80(m，6H)，7.89(d，2H)，7.96(dd，2H).
Embodiment 2
Present embodiment disclose structural formula following 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-p-propyl benzene carbazyl)] fluorenes (R is a propyl):
Figure BDA0000048394000000091
The preparation of above-mentioned target molecule is following:
One, 9,9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorenes
Figure BDA0000048394000000092
Under the argon shield, in the there-necked flask of 100mL, add 2 respectively, and the 7-dibromo fluorenone (3.303g, 9mmol), N-p-propyl phenyl carbazole (35.9g, 126mmol), methylsulphonic acid (0.9g, 9mmol).At 140 ℃ of following stirring reaction 6h, stopped reaction also is cooled to room temperature, uses dichloromethane extraction, more respectively with saturated sodium bicarbonate solution and distillation washing.Concentrate organic layer, obtain blue solid.Crude product obtains white solid product with acetone recrystallization after adopting sherwood oil/methylene dichloride (3: 1) to separate purification as leacheate through silica gel column chromatography again.Productive rate 75%.
1H-NMR(500MHz，CDCl 3)：7.21(m，2H)，7.32(m，4H)，7.39(d，4H)，7.45(m，2H)，7.53(d，2H)，7.55-7.60(m，8H)，7.65(d，4H)，7.96(s，2H)，8.0(d，2H).
Two, 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-p-propyl benzene carbazyl)] fluorenes
Figure BDA0000048394000000093
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, and (1.7mL 4.3mmol) is added drop-wise to 9 with n-Butyl Lithium (2.5M in hexane); 9-two [3 '-(N-p-propyl benzene carbazyl)]-2, (1.78g is in THF 2mmol) (100mL) solution for 7-dibromo fluorenes; Stir 3h down at-78 ℃, (0.8mL 4.3mmol) injects wherein rapidly through syringe with diphenyl phosphine chloride again; Obtain transparent pale yellow solution, be warming up to room temperature naturally after stirring reaction spend the night.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, uses anhydrous magnesium sulfate drying, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.With methylene dichloride (70mL) dissolving, add 30% ydrogen peroxide 50 (8mL), stirring reaction spends the night under the room temperature.Separate organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, obtain white solid and adopt ethyl acetate/methanol to obtain white solid product through silica gel column chromatography separation purification as leacheate.Productive rate is 30%.
1H-NMR(500MHz，CDCl 3)：7.16-7.21(m，6H)，7.29-7.32(m，8H)，7.38-7.41(m，8H)，7.45(m，2H)，7.55(m，4H)，7.59-7.62(m，12H)，7.76-7.80(m，6H)，7.89(d，2H)，7.96(dd，2H).
Embodiment 3
Present embodiment disclose structural formula following 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(the hot benzene carbazyl of N-p-)] fluorene derivatives (R is an octyl, straight chain):
Figure BDA0000048394000000101
The preparation of above-mentioned target molecule is following:
One, 9,9-two [3 '-(the hot benzene carbazyl of N-p-)]-2,7-dibromo fluorenes
Figure BDA0000048394000000111
Under the argon shield, in the there-necked flask of 100mL, add 2 respectively, and the 7-dibromo fluorenone (3.303g, 9mmol), the hot benzene carbazole of N-p-(42.9g, 126mmol), methylsulphonic acid (0.9g, 9mmol).At 140 ℃ of following stirring reaction 6h, stopped reaction also is cooled to room temperature, uses dichloromethane extraction, more respectively with saturated sodium bicarbonate solution and distillation washing.Concentrate organic layer, obtain blue solid.Crude product obtains white solid product with acetone recrystallization after adopting sherwood oil/methylene dichloride (3: 1) to separate purification as leacheate through silica gel column chromatography again.Productive rate 75%.
1H-NMR(500MHz，CDCl 3)：7.21(m，2H)，7.32(m，4H)，7.39(d，4H)，7.45(m，2H)，7.53(d，2H)，7.55-7.60(m，8H)，7.65(d，4H)，7.96(s，2H)，8.0(d，2H).
Two, 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(the hot benzene carbazyl of N-p-)] fluorenes
Figure BDA0000048394000000112
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, and (1.7mL 4.3mmol) is added drop-wise to 9 with n-Butyl Lithium (2.5M in hexane); 9-two [3 '-(the hot benzene carbazyl of N-p-)]-2, (2.06g is in THF 2mmol) (100mL) solution for 7-dibromo fluorenes; Stir 3h down at-78 ℃, (0.8mL 4.3mmol) injects wherein rapidly through syringe with diphenyl phosphine chloride again; Obtain transparent pale yellow solution, be warming up to room temperature naturally after stirring reaction spend the night.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, uses anhydrous magnesium sulfate drying, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.With methylene dichloride (70mL) dissolving, add 30% ydrogen peroxide 50 (8mL), stirring reaction spends the night under the room temperature.Separate organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, obtain white solid and adopt ethyl acetate/methanol to obtain white solid product through silica gel column chromatography separation purification as leacheate.Productive rate is 30%.
1H-NMR(500MHz，CDCl 3)：7.16-7.21(m，6H)，7.29-7.32(m，8H)，7.38-7.41(m，8H)，7.45(m，2H)，7.55(m，4H)，7.59-7.62(m，12H)，7.76-7.80(m，6H)，7.89(d，2H)，7.96(dd，2H).
Embodiment 4
Present embodiment disclose structural formula following 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-p-(6-dodecylbenzene) carbazyl)] fluorene derivatives (R is the twelve earthly branches alkyl group, side chain):
Figure BDA0000048394000000121
The preparation of above-mentioned target molecule is following:
One, 9,9-two [3 '-(N-p-(6-dodecylbenzene) carbazyl)]-2,7-dibromo fluorenes
Figure BDA0000048394000000122
Under the argon shield, in the there-necked flask of 100mL, add 2 respectively, and the 7-dibromo fluorenone (3.303g, 9mmol), N-p-(6-dodecylbenzene) carbazole (41.3g, 126mmol), methylsulphonic acid (0.9g, 9mmol).At 140 ℃ of following stirring reaction 6h, stopped reaction also is cooled to room temperature, uses dichloromethane extraction, more respectively with saturated sodium bicarbonate solution and distillation washing.Concentrate organic layer, obtain blue solid.Crude product obtains white solid product with acetone recrystallization after adopting sherwood oil/methylene dichloride (3: 1) to separate purification as leacheate through silica gel column chromatography again.Productive rate 75%.
1H-NMR(500MHz，CDCl 3)：7.21(m，2H)，7.32(m，4H)，7.39(d，4H)，7.45(m，2H)，7.53(d，2H)，7.55-7.60(m，8H)，7.65(d，4H)，7.96(s，2H)，8.0(d，2H).
Two, 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-p-(6-dodecylbenzene) carbazyl)] fluorenes
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, and (1.7mL 4.3mmol) is added drop-wise to 9 with n-Butyl Lithium (2.5M in hexane); 9-two [3 '-(N-p-(6-dodecylbenzene) carbazyl)]-2, (2.28g is in THF 2mmol) (100mL) solution for 7-dibromo fluorenes; Stir 3h down at-78 ℃, (0.8mL 4.3mmol) injects wherein rapidly through syringe with diphenyl phosphine chloride again; Obtain transparent pale yellow solution, be warming up to room temperature naturally after stirring reaction spend the night.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, uses anhydrous magnesium sulfate drying, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.With methylene dichloride (70mL) dissolving, add 30% ydrogen peroxide 50 (8mL), stirring reaction spends the night under the room temperature.Separate organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, obtain white solid and adopt ethyl acetate/methanol to obtain 2 of white, 7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorenes solid product through silica gel column chromatography separation purification as leacheate.Productive rate is 30%.
1H-NMR(500MHz，CDCl 3)：7.16-7.21(m，6H)，7.29-7.32(m，8H)，7.38-7.41(m，8H)，7.45(m，2H)，7.55(m，4H)，7.59-7.62(m，12H)，7.76-7.80(m，6H)，7.89(d，2H)，7.96(dd，2H).
Embodiment 5
Present embodiment adopts 2 among the embodiment 1,7-two (diphenyl phosphine oxygen base)-9, and 9-two [3 '-(N-phenyl carbazole base)] fluorenes blue phosphorescent material is as the application of the luminescent layer of organic electroluminescence device; The organic electroluminescence device of this laminate structure, its structure setting is followed successively by matrix, conductive layer, hole injection layer, hole transmission layer, luminescent layer, hole barrier-electron transfer layer and metal level; Wherein, in the present embodiment, matrix is a glass, and conductive layer is ITO, and metal level adopts the Mg:Ag alloy layer.
Organic electroluminescence device, as shown in Figure 2, its structure is arranged in order and is glass 11/ITO conductive layer 12/ hole injection layer 13/ transport layer 14/ luminescent layer 15/ hole barrier-electron transfer layer 16/Mg:Ag metal level 17; Wherein, the mol ratio of Mg and Ag is 10: 1.
The preparation technology of organic electroluminescence device is:
All material all, is carried out the device preparation after purifying in distillation;
Ito glass is successively through sanitising agent, deionized water, acetone, and ethanol to clean the back dry in baking oven;
Vapor deposition one deck hole injection layer m-MTDATA, vapor deposition hole transmission layer NPB, vapor deposition luminescent layer then then on the ito glass that cleans up; Luminescent layer is our synthetic 2; 7-two (diphenyl phosphine oxygen base)-9, the FIrpic phosphor material of 9-two [3 '-(N-phenyl carbazole base)] fluorenes material of main part doping different ratios, the TPBI that the about 40nm of vapor deposition last layer is thick again is as hole barrier/electron transfer layer; The lithium fluoride that in addition 1nm is thick strengthens electronics and injects, and negative electrode is the MAGNESIUM METAL 99 silver alloys.Organic layer and electrode are in 3 * 10 in cavity -5Vapor deposition under the vacuum tightness of Pa and, the vapor deposition speed of organic layer does
Figure BDA0000048394000000141
The vapor deposition speed of lithium fluoride does
Figure BDA0000048394000000142
The vapor deposition speed of argent does The test of all properties all is in the environment of normal pressure, room temperature, to record.Thickness is by near the quartz crystal oscillator sheet monitoring that is positioned at the substrate in the evaporate process, and proofreaies and correct through XP-2 step appearance (Ambios company).The light-emitting area of the organic electroluminescence device that makes is 2mm 2
Should be understood that above-mentioned statement to preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with accompanying claims.

Claims (10)

1. a kind of bipolarity blue light material of main part of formula:
Figure FDA0000048393990000011
In the formula, R is H or C 1～C 12Alkyl.
2. a kind of bipolarity blue light material of main part according to claim 1 is characterized in that said R is C 1～C 12Straight chained alkyl.
3. a kind of bipolarity blue light material of main part according to claim 1 is characterized in that said R is C 1～C 12Branched-chain alkyl.
4. the preparation method of a bipolarity blue light material of main part is characterized in that, comprises the steps:
Step S1, provide structural formula to do
Figure FDA0000048393990000012
2,7-dibromo fluorenone and structural formula do
Figure FDA0000048393990000013
N-phenyl carbazole verivate; In the formula, R is H or C 1～C 12Alkyl;
Step S2, in oxygen-free environment; With 2; 7-dibromo fluorenone, N-phenyl carbazole, methylsulphonic acid place reactor drum to carry out building-up reactions; Make structural formula for 9; 9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorene derivatives;
In step S3, the oxygen-free environment; With make among the step S2 9; 9-two [3 '-(N-phenyl carbazole base)]-2; 7-dibromo fluorene derivatives is dissolved in and forms solution in the organic solvent; In solution, drip n-Butyl Lithium subsequently, add again behind the stirring reaction diphenyl phosphine chloride proceed the reaction after, make structural formula for 2; 7-two (diphenyl phosphine oxygen base)-9, the said bipolarity blue light material of main part of 9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives.
5. preparation method according to claim 4 is characterized in that, among the said step S1, R is C 1～C 12Straight chained alkyl.
6. preparation method according to claim 4 is characterized in that, among the said step S1, R is C 1～C 12Branched-chain alkyl.
7. preparation method according to claim 4 is characterized in that, among the said step S2, also comprises 9, and 9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorene derivatives purification process process, treatment step is following:
S21, earlier with methylene dichloride to 9,9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorene derivatives carries out extraction treatment, respectively with saturated sodium bicarbonate solution and distillation washing, concentrated organic layer obtains the blue solid crude product again;
After S22, blue solid crude product adopt sherwood oil/methylene dichloride (mol ratio is 3: 1) to separate purification as leacheate through silica gel column chromatography; Use acetone recrystallization again; It is purified 9 to obtain white, 9-two [3 '-(N-phenyl carbazole base)]-2,7-dibromo fluorene derivatives solid.
8. preparation method according to claim 4 is characterized in that, among the said step S3, organic solvent is at least a in THF, the ether.
9. according to claim 4 or 8 described preparing methods, it is characterized in that, among the said step S3, also comprise 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives treating processes, treatment step is following:
S31, with 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives spends the night, ethyl acetate extraction is adopted in then water cancellation reaction, concentrates organic layer, use anhydrous magnesium sulfate drying, arrive solid crude product;
S32, solid crude product adopt sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtain white solid product;
S33, dissolve white solid product with methylene dichloride, add ydrogen peroxide 50, stirring reaction spends the night under the room temperature; Separate organic layer, respectively with saturated aqueous common salt and distillation washing; Revolve the steaming solvent, obtain white solid and adopt ethyl acetate/methanol to separate through silica gel column chromatography to purify that to obtain white purified 2,7-two (diphenyl phosphine oxygen base)-9,9-two [3 '-(N-phenyl carbazole base)] fluorene derivatives solid as leacheate.
10. organic electroluminescence device, said organic electroluminescence device is a laminate structure, this laminate structure setting is followed successively by matrix, conductive layer, hole injection layer, hole transmission layer, luminescent layer, hole barrier-electron transfer layer and metal level; It is characterized in that said luminescent layer is the described bipolarity blue light of claim 1 material of main part.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102911658A (en) * 2012-11-02 2013-02-06 黑龙江大学 Nine-site functional fluorenyl aromatic single-phosphine oxide electroluminescent material and preparation method thereof
CN103897689A (en) * 2012-12-27 2014-07-02 海洋王照明科技股份有限公司 Organic electroluminescent material, preparation method thereof and organic electroluminescent device
CN103952140A (en) * 2013-12-04 2014-07-30 宁波大学 Bipyridine carbazole fluorescent material
CN104017565A (en) * 2013-02-28 2014-09-03 海洋王照明科技股份有限公司 Bipolar blue-phosphorescence material, preparation method thereof and organic electroluminescent device
CN104017559A (en) * 2013-02-28 2014-09-03 海洋王照明科技股份有限公司 Bipolar blue-phosphorescence material, preparation method thereof and organic electroluminescent device
CN104250248A (en) * 2013-06-26 2014-12-31 海洋王照明科技股份有限公司 Bipolar blue phosphorescent compound, preparation method thereof and organic electroluminescent device
CN104250550A (en) * 2013-06-26 2014-12-31 海洋王照明科技股份有限公司 Bipolar copolymer blue light phosphorescent body material, preparation method thereof and organic electroluminescent device

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101460588A (en) * 2006-05-31 2009-06-17 默克专利有限公司 New materials for organic electroluminescent devices

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101460588A (en) * 2006-05-31 2009-06-17 默克专利有限公司 New materials for organic electroluminescent devices

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FANG-MING HSU,ET AL.: "《Phosphine-Oxide-Containing Bipolar Host Material for Blue Electrophosphorescent Devices》", 《CHEM.MATER.》, vol. 21, no. 6, 19 February 2009 (2009-02-19), pages 1017 - 1022 *
FANG-MING HSU，ET AL.: "A Bipolar Host Material Containing Triphenylamine and Diphenylphosphoryl-Substituted Fluorene Units for Highly Efficient Blue Electrophosphorescence", 《ADV. FUNCT. MATER》, vol. 19, 24 July 2009 (2009-07-24), pages 2834 - 2843, XP001548785, DOI: 10.1002/afdm.200900703 *
SILU TAO ET AL.: "High-Efficiency Nondoped Deep-Blue-Emitting Organic Electroluminescent Device", 《CHEM.MATER.》, vol. 22, 29 January 2010 (2010-01-29), pages 2138 - 2141 *

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CN103897689B (en) * 2012-12-27 2016-06-01 海洋王照明科技股份有限公司 Electroluminescent organic material and its preparation method and organic electroluminescence device
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CN103952140A (en) * 2013-12-04 2014-07-30 宁波大学 Bipyridine carbazole fluorescent material

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