CN102372843B - Fluorene-containing organic semiconductor materials, and preparation method and application thereof - Google Patents

Fluorene-containing organic semiconductor materials, and preparation method and application thereof Download PDF

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CN102372843B
CN102372843B CN 201010258003 CN201010258003A CN102372843B CN 102372843 B CN102372843 B CN 102372843B CN 201010258003 CN201010258003 CN 201010258003 CN 201010258003 A CN201010258003 A CN 201010258003A CN 102372843 B CN102372843 B CN 102372843B
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fluorenes
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CN102372843A (en
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周明杰
黄杰
黄佳乐
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
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Abstract

The invention belongs to the field of optoelectronic materials and discloses fluorene-containing organic semiconductor materials. The fluorene-containing organic semiconductor materials have the general formula (P) shown in the specifications, wherein n is an integer between 1 and 100; m is an integer between 1 and 20; x and y are positive real values, and (x+y) is equal to 1; R1 and R2 are hydrogen, fluorine, cyano, C1-C40 alkyl, alkoxy, aryl or heteroaryl respectively; and R3 is hydrogen, phenyl, C1-C20 alkyl or C1-C40 arylalkoxy. The invention also provides a preparation method for the fluorene-containing organic semiconductor materials and application of the fluorene-containing organic semiconductor materials. The fluorene-containing organic semiconductor materials have high carrier mobility, high absorbance and wide light absorption range; the sunlight utilization rate of the materials is improved; and the preparation method is simple, high in yield, and easy to operate and control.

Description

One class contains fluorenes organic semiconductor material and its preparation method and application
Technical field
The present invention relates to a kind of multipolymer, relate to a class more specifically and contain the fluorenes organic semiconductor material.
The invention still further relates to a class and contain preparation method and the application thereof of fluorenes organic semiconductor material.
Background technology
High efficiency solar cell normally is raw material with the inorganic semiconductor, but main silicon wafer solar cell is because the production process technology complexity is seriously polluted in the market, and power consumption is big, and the cost height has suppressed the development of its commercial applications.Therefore utilize cheap material preparation low cost, dynamical solar cell is research focus and the difficult point in photovoltaic field always.And organic semiconductor material is on the one hand because the environmental stability of organic materials is good, preparation cost is low, function is easy to modulation, snappiness and film-forming properties are all better; On the other hand because the organic solar batteries course of processing is simple relatively, but cold operation, and the element manufacturing cost is advantage such as lower and receiving much concern also, becomes cheap and attractive solar cell material.In addition, the potential advantages of organic solar batteries also comprise: can realize the big area manufacturing, can use flexible substrate, environmental friendliness, light portable etc.
Though organic solar batteries has obtained development faster, but it is still much lower than the efficiency of conversion of inorganic solar cell, the main restricting factor that limits its performance raising has: the carrier mobility that organic semiconductor device is relatively low, the spectral response of device and solar radiation spectrum do not match, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.In order to make organic solar batteries obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Fluorenes is owing to have the planar molecule characteristic, and structure is rigidity comparatively, so chemical property is stable; And can introduce other side chains at 9 by chemical reaction, easily carry out the transition metal cross-coupling on 2,7, therefore have good chemical modifiability; It also has relatively wideer band gap and lower HOMO energy level in addition, good quantum yield, hole transport performance and film-forming properties, so fluorenes and derivative thereof are widely used in the research of photoelectric material.
Anthracene and derivative thereof have good stability and film-forming properties preferably; Its uv-vis spectra presents wideer finger peak and absorbs, and is conducive to improve the absorption coverage to sunlight; And it has suitable carrier transmission characteristics, and hole mobility can reach 3cm under its crystal room temperature 2/ Vs is the organic semiconductor material of a class excellence.Though anthracene and derivative thereof are existing a lot of as the report of electroluminescent organic material, rarely have report as the research of organic photovoltaic material, this has just limited its range of application greatly.
And thieno-[3,4-c] pyrroles-4,6-diketone simple in structure, atom site relative compact in the molecule, and structure has symmetry, when as the conjugated polymers unit, very strong electrophilic effect arranged also.By increasing alkane chain at pyrrole ring, also can increase solvability and the processibility of conjugated polymers well.At present, it is with a wide range of applications in the organic photoelectric research field.
Summary of the invention
The object of the present invention is to provide a class to contain the fluorenes organic semiconductor material, be used for addressing the above problem.
The present invention also aims to provide a class to contain the preparation method of fluorenes organic semiconductor material, and this organic semiconductor material is at polymer solar battery, organic electroluminescence device, organic field effect tube, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser material.
A class of the present invention contains the fluorenes organic semiconductor material and has following general formula (P):
In the formula, n is the integer between 1～100; M is 1～20 integer; The span of preferred m is: 6～12 integer;
X, y are real positive value, and x+y=1; And x+y=1; The numerical value of x, y is determined by the feed ratio of three kinds of cell cubes;
R 1, R 2Be respectively hydrogen, fluorine, cyano group, C 1～C 40Alkyl, alkoxyl group, aryl or heteroaryl; Preferred R 1, R 2Be respectively C 1～C 18Alkyl;
R 3Be hydrogen, phenyl, C 1～C 20Alkyl or C 1～C 40Alkoxy aryl; Preferred described R 3Be C 1～C 12Alkyl, or C 6～C 40Alkoxy aryl.
The designed class of the present invention contains the fluorenes organic semiconductor material, and its preparation scheme is as follows:
Step 1: under the anhydrous and oxygen-free reaction conditions, with 2,7-, two bromo-9,9-dialkyl group fluorenes and n-Butyl Lithium (n-BuLi) are added in second solvent with mol ratio 1: 2～4 under-70 ℃～-85 ℃, add 2-isopropoxy-4,4,5 then, 5-tetramethyl--1,3,2-, two assorted oxygen pentaboranes or two tetramethyl ethylene ketone close two boron, carry out condensation reaction 12～48 hours, obtain product, namely 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes; Wherein, second solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the mole dosage that the assorted oxygen pentaboranes of 2-two or two tetramethyl ethylene ketone close two boron is 2,7-, two bromo-9,2～4 times of 9-dialkyl group fluorenes; The condensation reaction formula is as follows:
Figure BSA00000236819200031
Step 2: in oxygen-free environment, with 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof, thieno-[3,4-c] pyrroles-4,6-diketone or derivatives thereof m: j: k in molar ratio mixes, and satisfy m=j+k, under 70～100 ℃, catalyzer, alkali lye and first solvent, carry out Suzuki reaction 24～72 hours, obtain described organic semiconductor material; Wherein, catalyzer is Pd (PPh 3) 4, Pd (OAc) 2, tricyclohexyl phosphine, Pd 2(dba) 3/ P (o-Tol) 3Or Pd (PPh 3) 2Cl 2Alkali lye is the NaOH aqueous solution, Na 2CO 3The aqueous solution, NaHCO 3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, first solvent is toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc., catalyst consumption is 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.01%～20% of 9-dialkyl group fluorenes molar weight, the consumption of alkali are 2,7-two (4,4,5,5-tetramethyl--1, the assorted oxygen pentaboranes of 3,2-two) base-9,5～10 times of 9-dialkyl group fluorenes molar weight; The Suzuki reaction formula is as follows:
Figure BSA00000236819200041
The present invention compared with prior art possesses following advantage at least:
1. introduced anthracene and thieno-[3,4-c] pyrroles-4 in the organic semiconductor material molecule of the present invention, 6-diketone group has obviously improved its carrier mobility performance and light abstraction width;
2. contain the anthracene unit in the organic semiconductor material molecule of the present invention, because its good planeness and conjugation degree, thereby improved its carrier mobility, simultaneously, thieno-[3,4-c] pyrroles-4 has introduced modifications such as alkyl for 5 on the 6-diketone, improve its solvability, thereby improved its processing characteristics;
3. thieno-[3,4-c] pyrroles-4,6-diketone simple in structure, atom site relative compact in the molecule, and structure has symmetry, when as the conjugated polymers unit, has very strong electrophilic effect.Adopt thieno-[3,4-c] pyrroles-4,6-diketone unit and anthracene unit and the copolymerization of fluorenes unit, effectively regulate the band gap of this organic semiconductor material, and push to infrared its energy of absorption edge and the near-infrared region, make its absorbancy strong, wide to light abstraction width, improve its utilization ratio to sunlight, simultaneously, made this organic semiconductor material solubility property and charge transport properties excellence;
4. this organic semiconductor material preparation method technology is simple, the productive rate height, and the reaction conditions gentleness is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is with the structural representation of the multipolymer among the present invention as the organic solar batteries device of active coating;
Fig. 2 is with the structural representation of the multipolymer among the present invention as the organic electroluminescence device of luminescent layer;
Fig. 3 is with the structural representation of the multipolymer among the present invention as the organic field effect tube of organic semiconductor layer.
Embodiment
A class provided by the invention contains the fluorenes organic semiconductor material, has following general formula (P):
Figure BSA00000236819200051
In the formula, n is the integer between 1～100; M is 1～20 integer; The span of preferred m is: 6～12 integer
X, y are real positive value, and x+y=1; And x+y=1; The numerical value of x, y is determined by the feed ratio of three kinds of cell cubes;
R 1, R 2Can be identical or different during appearance, the expression list replaces or polysubstituted functional group independently of one another, and is selected from straight chain or branched alkyl or alkoxyl group, optional replacement or unsubstituted aryl or the heteroaryl of hydrogen atom, fluorine atom, cyano group, optional replacement or the unsubstituted 1-18 of having a C atom; Preferred R 1, R 2Be respectively C 1～C 18Alkyl;
R 3Be hydrogen, phenyl, C 1～C 20Alkyl or C 1～C 40Alkoxy aryl; Preferred described R 3Be C 1～C 12Alkyl, or C 6～C 40Alkoxy aryl.
One class contains the fluorenes organic semiconductor material, and its preparation scheme is as follows:
Step S1: under the anhydrous and oxygen-free reaction conditions, with 2,7-, two bromo-9,9-dialkyl group fluorenes and n-Butyl Lithium were added in second solvent with mol ratio under-70 ℃～-85 ℃ in 1.0: 2.0～1.0: 4.0, added 2-isopropoxy-4,4 then, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes or two tetramethyl ethylene ketone close two boron, and (its mole dosage is 2,7-two bromo-9,2.0～4.0 times of 9-dialkyl group fluorenes), reacted 12～48 hours, obtain product, namely 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes; Wherein second solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate, and its reaction formula is as follows:
Figure BSA00000236819200061
Or
Figure BSA00000236819200062
Step S2: in oxygen-free environment, with 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof, thieno-[3,4-c] pyrroles-4,6-diketone or derivatives thereof m: j: k in molar ratio mixes, and satisfies m=j+k, under 70～100 ℃, catalyzer, alkali lye and first solvent, carry out Suzuki reaction 24～72 hours, obtain polymkeric substance; Wherein, catalyzer is Pd (PPh 3) 4, Pd (OAc) 2, tricyclohexyl phosphine, Pd 2(dba) 3/ P (o-Tol) 3Or Pd (PPh 3) 2Cl 2Alkali lye is the NaOH aqueous solution, Na 2CO 3The aqueous solution, NaHCO 3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, first solvent is toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc., catalyst consumption is 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.01%～20% of 9-dialkyl group fluorenes molar weight, the consumption of alkali are 2,7-two (4,4,5,5-tetramethyl--1, the assorted oxygen pentaboranes of 3,2-two) base-9,5～10 times of 9-dialkyl group fluorenes molar weight; Its reaction formula is as follows:
Figure BSA00000236819200071
Oxygen-free environment of the present invention is by nitrogen (N 2) and/or rare gas element mixing formation.
The present invention has developed a kind of organic semiconductor material that contains fluorenes, and is applied to fields such as organic solar batteries.This material has lower energy gap, higher mobility, and the absorption region of spectrum is wide, and this material is conducive to current carrier and more effectively transmits in active layer material inside.With the organic solar batteries of the material among the present invention as the active material preparation, through behind the high temperature annealing, can effectively increase order and the regularity arranged between each group of intramolecularly and molecule segment, improve transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The open following class of structure of present embodiment contains fluorenes organic semiconductor material P1, P2:
Figure BSA00000236819200072
P1 x＝0.1，y＝0.9
P2 x＝0.5，y＝0.5
The preparation process of P1, P2 is as follows:
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Figure BSA00000236819200081
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N 2Protection under, add 2 of white in the there-necked flask, 7-two bromo-9,9-dioctyl fluorene 9.0mmol injects the refining tetrahydrofuran solvent of 150ml with syringe, slowly injects 27.0mmol n-BuLi with syringe again under-78 ℃ of conditions, stirring reaction 2 hours.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and steam solvent.At last with the crude product sherwood oil: ethyl acetate (v/v=15: 1) separate for leacheate carries out silica gel column chromatography, obtain pulverulent solids 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene, productive rate 65%.GC-MS(EI-m/z)：642(M +)。
The preparation of step 2, P1, P2:
Figure BSA00000236819200082
P1 x＝0.1，y＝0.9
P2 x＝0.5，y＝0.5
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.1mmol, 1,3-two bromo-thieno-[3,4-c] pyrroles-4, the Na of 6-diketone 0.9mmol, tetra-triphenylphosphine palladium 0.025mmol, 2mol/L 2CO 3Aqueous solution 5ml and toluene solvant 30ml are by leading to N repeatedly 2Make reaction system be in anaerobic state with vacuumizing, under 70 ℃ of conditions, react 72h.
Behind the reaction 72h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml, it is splashed into constantly stirring in the 300ml anhydrous methanol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 1 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 1 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 54200, the polymkeric substance monodispersity is that 1.38, n is 100.
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.5mmol, 1,3-two bromo-thieno-s [3,4-c] pyrroles-4,6-diketone 0.5mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 2.Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 2 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 35900, the polymkeric substance monodispersity is that 1.56, n is 65.
Embodiment 2
The open following class of structure of present embodiment contains fluorenes organic semiconductor material P3, P4:
Figure BSA00000236819200091
P3 x＝0.8，y＝0.2
P4 x＝0.2，y＝0.8
The preparation process of P3, P4 is as follows:
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dihexyl fluorenes:
Step 1 in its preparation process reference example 1 just makes up the oxygen-free environment protective atmosphere with argon gas.
The preparation of step 3, P3, P4:
Figure BSA00000236819200101
P3 x＝0.8，y＝0.2
P4 x＝0.2，y＝0.8
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dihexyl fluorenes 1mmol, 9,10-two bromo-2, (the synthetic method of this compound is referring to people's such as Klaus Mullen Macromol.Chem.Phys.2006 for 6-two (2-octyl-decyl) anthracene 0.8mmol, 207,1107-1115), 1,3-two bromo-5-methyl-thieno-s [3,4-c] pyrroles-4, the Na of 6-diketone 0.2mmol, palladium 3mg, 2mol/L 2CO 3Aqueous solution 10ml and toluene solvant 40ml make reaction system be in anaerobic state by leading to argon gas repeatedly and vacuumizing, and react 24h under 100 ℃ of conditions.
Behind the reaction 24h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 3 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 3 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 34600, the polymkeric substance monodispersity is that 2.27, n is 38.
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dihexyl fluorenes 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.2mmol, 1,3-two bromo-5-methyl-thieno-[3,4-c] pyrroles-4,6-diketone 0.8mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 4.Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 4 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 25800, the polymkeric substance monodispersity is that 2.23, n is 43.
Embodiment 3
The open following class of structure of present embodiment contains fluorenes organic semiconductor material P5, P6:
P5 x＝0.5，y＝0.5
P6 x＝0.6，y＝0.4
The preparation process of P5, P6 is as follows:
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-two (dodecyl) fluorenes:
Step 1 in its preparation process reference example 1 just makes up the oxygen-free environment protective atmosphere with nitrogen and argon gas gas mixture.
The preparation of step 2, P5, P6:
P5 x＝0.5，y＝0.5
P6 x＝0.6，y＝0.4
Figure BSA00000236819200121
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-two (dodecyl) fluorenes 1mmol, 9, (synthetic method of this compound is referring to people's such as Elimelech Rochlin J.Org.Chem. for 10-two bromo-2-fluorine anthracene 0.5mmol, 2003,68,216-226), 1,3-two bromo-5-octyl group-thieno-s [3,4-c] pyrroles-4, the Na of 6-diketone 0.5mmol, tetra-triphenylphosphine palladium 0.02mmol, 2mol/L 2CO 3Aqueous solution 10ml and toluene solvant 40ml by leading to nitrogen and argon gas gas mixture repeatedly, and vacuumize and make reaction system be in anaerobic state, react 58h under 80 ℃ of conditions.
Behind the reaction 58h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 5 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 5 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 18200, the polymkeric substance monodispersity is that 2.43, n is 25.Purple
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-two (dodecyl) fluorenes 1mmol, 9,10-two bromo-2-fluorine anthracene 0.6mmol, 1,3-two bromo-5-octyl group-thieno-s [3,4-c] pyrroles-4,6-diketone 0.4mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 6.Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 6 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 19500, the polymkeric substance monodispersity is that 2.06, n is 27.
Embodiment 4
The open following class of structure of present embodiment contains fluorenes organic semiconductor material P7, P8:
Figure BSA00000236819200131
P7 x＝0.5，y＝0.5
P8 x＝0.4，y＝0.6
The preparation process of P7, P8 is as follows:
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Step 1 in its preparation process reference example 1.
The preparation of step 2, P7, P8:
P7 x＝0.5，y＝0.5
P8 x＝0.4，y＝0.6
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-1, (synthetic method of this compound is referring to people's such as Osman Cakmak J.Org.Chem., 2006,71 for 4-dimethoxy anthracene 0.5mmol, 1795-1801), 1,3-two bromo-5-(2-ethylhexyl)-thieno-[3,4-c] pyrroles-4, the Na of 6-diketone 0.5mmol, tricyclohexyl phosphine 5mg, 2mol/L 2CO 3Aqueous solution 10ml and toluene solvant 50ml are by leading to N repeatedly 2Make reaction system be in anaerobic state with vacuumizing, under 90 ℃ of conditions, react 64h.
Behind the reaction 64h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 7 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 7 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 50700, the polymkeric substance monodispersity is that 1.53, n is 73.
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-1,4-dimethoxy anthracene 0.4mmol, 1,3-two bromo-5-(2-ethylhexyl)-thieno-[3,4-c] pyrroles-4,6-diketone 0.6mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 8.Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 8 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 41800, the polymkeric substance monodispersity is that 1.31, n is 60.
Embodiment 5
The open following class of structure of present embodiment contains fluorenes organic semiconductor material P9, P10:
Figure BSA00000236819200151
P9 x＝0.5，y＝0.5
P10 x＝0.1，y＝0.9
The preparation process of P9, P10 is as follows:
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Step 1 in its preparation process reference example 1.
The preparation of step 2, P9, P10:
Figure BSA00000236819200161
P9 x＝0.5，y＝0.5
P10 x＝0.1，y＝0.9
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2-octyl groups-6-octadecane oxygen base anthracene 0.5mmol, 1,3-two bromo-5-dodecyl-thieno-[3,4-c] pyrroles-4, the Na of 6-diketone 0.5mmol, tetra-triphenylphosphine palladium 0.02mmol, 2mol/L 2CO 3Aqueous solution 10ml and toluene solvant 50ml are by leading to N repeatedly 2Make reaction system be in anaerobic state with vacuumizing, under 75 ℃ of conditions, react 40h.
Behind the reaction 40h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 9 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 9 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 27300, the polymkeric substance monodispersity is that 1.73, n is 33.
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-2-octyl groups-6-octadecane oxygen base anthracene 0.1mmol, 1,3-two bromo-5-(2-ethylhexyl)-thieno-[3,4-c] pyrroles-4,6-diketone 0.9mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 10.Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 10 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 22000, the polymkeric substance monodispersity is that 2.01, n is 30.
The present invention also provides a class to contain the fluorenes organic semiconductor material at polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser.
Following examples are that a class contains the fluorenes organic semiconductor material at organic solar batteries, organic field effect tube, the application in the organic electroluminescence device.
Embodiment 6
With the organic solar batteries device of the P1 among the embodiment one as active layer material
A kind of organic solar batteries device, its structure as shown in Figure 1.Wherein, the substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic solar batteries device is: glass 11/ITO layer 12/PEDOT:PSS layer 13/ active coating 14/Al layer 15; Wherein, the material of active coating is mixture, comprises electron donor material, and PCBM is electron acceptor material; Electron donor material is material with the P1 among the embodiment one, and electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate (being called for short PCBM); ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid); Preferred square resistance is the ITO of 18 Ω/mouths.
This organic solar batteries preparation of devices process is:
Tin indium oxide (ITO) layer 12 in that surface deposition one deck square resistance of glass substrate 11 is 10-20 Ω/mouth forms the conductive layer as anode, and thickness is about 50-300nm;
Ito glass process ultrasonic cleaning, and with after oxygen-Plasma processing, be coated with the PEDOT:PSS layer 13 that last layer plays modification on the ITO surface, thickness is 50-300nm;
Adopt spin coating technique to apply one deck active coating 14 at poly-(3,4-Ethylenedioxy Thiophene): PSS on (styrene sulfonic acid) layer for gathering, thickness is 50-300nm, and the material of this active coating is with the P1 among the embodiment one and [6,6] phenyl-C 61The mixture of-methyl-butyrate (being called for short PCBM);
At the surface vacuum evaporation metal aluminium of active coating, form the metal aluminium lamination 15 as negative electrode, obtain the organic solar batteries device;
With the organic solar batteries device with epoxy encapsulation after, place under 110 ℃ of air tight conditions annealing 1.5 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
The thickness of preferred ITO, PEDOT:PSS layer, active coating, Al layer is respectively 150nm, 50nm, 120nm, 100nm.
Embodiment 7
With the P1 among the embodiment one as the luminescent layer single layer device
A kind of organic electroluminescence device, its structure is as shown in Figure 2; Substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic electroluminescence device is: glass 21/ITO layer 22/ luminescent layer 23/LiF buffer layer 24/Al layer 25; Wherein: luminescent layer is material with the P1 among the embodiment one.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) layer 22 in that surface deposition one deck square resistance of glass substrate 21 is 10-20 Ω/mouth forms the conductive layer as anode, and thickness is 50-300nm; Preferred square resistance is the ITO of 10 Ω/mouths.
Be the luminescent layer 23 of material at ITO surface preparation one deck with the P1 among the embodiment one by spin coating technique, thickness is about 50-300nm;
Vacuum evaporation LiF on luminescent layer, as buffer layer 14, thickness is about 0.3-2nm;
Vacuum evaporation metallic aluminium on described luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains described organic electroluminescence device.
Embodiment 8
Be the organic field effect tube of material with the P1 that contains among the embodiment one
A kind of organic field effect tube, its structure is as shown in Figure 3; Substrate in the present embodiment adopts doped silicon wafer (Si) as substrate.
The structure of this organic field effect tube is: the SiO that Si 31/440nm is thick 2Insulation layer 32/ is used for modifying SiO 2Octadecyl trichlorosilane (OTS) layer 33/ organic semiconductor layer 34/ be source electrode (S) 35 and the drain electrode (D) 36 of material with the gold; Wherein, organic semiconductor layer is material with the P1 among the embodiment one; Wherein, source electrode (S) and drain electrode (D) material also can be selected copper material for use.
The preparation process of this organic field effect tube is:
At first, apply one deck SiO on a surface cleaning doped silicon wafer 31 later 2Insulation layer 32; Secondly, at described SiO 2Apply the octadecyl trichlorosilane layer 33 that one deck plays modification on the insulation layer, thickness is 10-200nm; Then, spin coating one deck is the organic semiconductor layer 34 of material with the P1 among the embodiment one on described octadecyl trichlorosilane layer, and thickness is about 50-300nm; At last, described organic semiconductor layer be arranged at intervals with the gold but be not limited only to source electrode (S) 35 and the drain electrode (D) 36 that gold is material, obtain described organic field effect tube.
Should be understood that above-mentioned statement at 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 claims.

Claims (10)

1. a class of following general formula (P) contains the fluorenes organic semiconductor material:
Figure FDA00003030557500011
In the formula, n is the integer between 1～100; M is 1～20 integer;
X, y are real positive value, and x+y=1;
R 1, R 2Be respectively hydrogen, fluorine, cyano group, C 1～C 40Alkyl, alkoxyl group, aryl or heteroaryl; R 3Be hydrogen, phenyl, C 1～C 20Alkyl or C 1～C 40Alkoxy aryl.
2. a class according to claim 1 contains the fluorenes organic semiconductor material, it is characterized in that, the span of described m is: 6～12 integer; Described R 1, R 2Be respectively C 1～C 18Alkyl; Described R 3Be C 1～C 12Alkyl, or C 6～C 40Alkoxy aryl.
3. a class contains the preparation method of fluorenes organic semiconductor material, it is characterized in that, comprises the steps:
In oxygen-free environment, with structural formula be
Figure FDA00003030557500012
2,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) base-9,9-dialkyl group fluorenes, structural formula are
Figure FDA00003030557500013
9,10-dibromoanthracene or derivatives thereof and structural formula are
Figure FDA00003030557500021
Thieno-[3,4-c] pyrroles-4,6-diketone or derivatives thereof, m:j:k mixes in molar ratio, and satisfies m=j+k, under 70～100 ℃, catalyzer, alkali lye and first solvent condition, carries out Suzuki reaction 24～72 hours, obtains structural formula and is
Figure FDA00003030557500022
A described class contain the fluorenes organic semiconductor material; Wherein,
N is 1～200 integer, and m is 1～20 integer;
X, y are arithmetic number, and x+y=1;
R 1, R 2Be hydrogen, fluorine, cyano group, C 1～C 40Alkyl, alkoxyl group, aryl or heteroaryl; R 3Be hydrogen, phenyl, C 1～C 20Alkyl or C 1～C 40Alkoxy aryl.
4. preparation method according to claim 3 is characterized in that, the span of described m is 6～12 integer; Described R 1, R 2Be respectively C 1～C 18Alkyl; Described R 3Be C 1～C 12Alkyl, or C 6～C 40Alkoxy aryl.
5. preparation method according to claim 3 is characterized in that, also comprise described 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation process of 9-dialkyl group fluorenes, preparation process is as follows:
In the anhydrous and oxygen-free condition, with structural formula be
Figure FDA00003030557500023
2,7-two bromo-9,9-dialkyl group fluorenes and n-Butyl Lithium are added in second solvent with mol ratio 1:2～4 under-70 ℃～-85 ℃, add structural formula then and are
Figure FDA00003030557500031
Two tetramethyl ethylene ketones close two boron or structural formula is
Figure FDA00003030557500032
2-isopropoxy-4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two carried out condensation reaction 12～48 hours, obtained structural formula and were
Figure FDA00003030557500033
Described 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes.
6. preparation method according to claim 5 is characterized in that, described second solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; Described 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the molar weight that the assorted oxygen pentaboranes of 2-two or two tetramethyl ethylene ketone close two boron is 2,7-, two bromo-9,2～4 times of 9-dialkyl group fluorenes.
7. preparation method according to claim 3 is characterized in that, the mole dosage of described catalyzer is 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.01%～20% of 9-dialkyl group fluorenes;
Described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand;
Described organic palladium is Pd (PPh 3) 4, Pd (OAc) 2, Pd 2(dba) 3Or Pd (PPh 3) 2Cl 2
Described organophosphor ligand is tricyclohexyl phosphine or P (o-Tol) 3
8. preparation method according to claim 7 is characterized in that, in the mixture of described organic palladium and organophosphor ligand, the mol ratio of described organic palladium and organophosphor ligand is 1:1～20.
9. preparation method according to claim 3 is characterized in that, described alkali lye is the NaOH aqueous solution, Na 2CO 3The aqueous solution, NaHCO 3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; The consumption of alkali is 2,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) base-9 in the described alkali lye, 5～10 times of 9-dialkyl group fluorenes molar weight; Described first organic solvent is at least a in toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate.
10. a class as claimed in claim 1 contains the fluorenes organic semiconductor material at organic solar batteries, organic electroluminescence device, organic field effect tube, organic optical storage, organic non-linear optical properties and organic laser material Application for Field.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
US6800381B2 (en) * 2001-10-26 2004-10-05 Korea Institute Of Science And Technology Fluorene compound, polymers thereof having a polyphenylene group, and EL element comprising the same
CN1852933A (en) * 2003-09-20 2006-10-25 科文有机半导体有限公司 White-emitting copolymers, representation and use thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800381B2 (en) * 2001-10-26 2004-10-05 Korea Institute Of Science And Technology Fluorene compound, polymers thereof having a polyphenylene group, and EL element comprising the same
CN1852933A (en) * 2003-09-20 2006-10-25 科文有机半导体有限公司 White-emitting copolymers, representation and use thereof

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