CN102453228A - Organic semiconductor material containing fluorene, anthracene and benzodithiophene units, preparation method, and application thereof - Google Patents
Organic semiconductor material containing fluorene, anthracene and benzodithiophene units, preparation method, and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of photo-electronic materials, and discloses an organic semiconductor material containing fluorene, anthracene and benzodithiophene units. The material is represented by a general formula (P), wherein n is an integer of 1-100, m is an integer of 1-20, x and y are positive real numbers, and x+y=1. R1 and R2 are respectively hydrogen, fluorine, cyan, C1-C40 straight chain or branched chain alkyl, or C1-C40 straight chain or branched chain alkoxy, aryl or heteroaryl. R3 is C1-C20 alkyl. The invention also provides a preparation method and an application of the organic semiconductor material containing fluorene, anthracene and benzodithiophene units. The organic semiconductor material provided by the invention is advantaged in high carrier mobility, high absorbance, high luminous absorption scope, and improved sunlight utilization rate. The preparation method is advantaged in simple technology, high yield, easy operation, and easy controlling.
Description
Technical field
The present invention relates to a kind of organic semiconductor material, relate to one type of usefulness more specifically and contain fluorenes, anthracene and benzo two thiophene unit organic semiconductor material.
The invention still further relates to one type of preparation method and application thereof that contains fluorenes, anthracene and benzo two thiophene unit organic semiconductor material.
Background technology
High efficiency solar cell normally is raw material with the inorganic semiconductor, but main in the market silicon wafer solar cell is seriously polluted owing to production process technology is complicated, and power consumption is big, and cost is high, has suppressed the development of its commercial applications.Therefore utilize cheap material preparation low cost, dynamical solar cell is photovoltaic hot research fields and difficult point 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 advantage such as the element manufacturing cost is also lower and receiving much concern 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 on 9, introduce other side chain through chemical reaction, be prone to carry out the transition metal cross-coupling on 2,7, so have the good chemical modifiability; It also has the band gap of relative broad and lower HOMO energy level in addition, good quantum yield, hole transport performance and film-forming properties, so fluorenes and verivate thereof are widely used in the research of photovaltaic material.
Anthracene and verivate thereof have good stability and film-forming properties preferably; The finger peak that its uv-vis spectra demonstrates broad absorbs, and helps improving the absorption coverage to sunshine; 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 one type of excellence.Though anthracene and verivate thereof are existing a lot of as the report of electroluminescent organic material, rarely have report as the research of organic photovoltaic material, this just big limitations its range of application.
Summary of the invention
The object of the present invention is to provide one type to contain fluorenes, anthracene and benzo two thiophene unit organic semiconductor material, be used to address the above problem.
One type of the present invention contains fluorenes, anthracene and benzo two thiophene unit organic semiconductor material, 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: the integer between 6≤m≤12;
X, y are real positive value, and x+y=1; The numerical value of x, y is by the feed ratio decision of three kinds of cell cubes;
R
1, R
2Be respectively hydrogen, fluorine, cyanic acid identical or inequality, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; Preferred R
1, R
2Optional replace or unsubstitutedly have a C
1～C
18Straight chain or branched alkyl or alkoxyl group, the optional replacement or unsubstituted aryl or heteroaryl;
R
3Be C
1～C
20Alkyl; Preferred R
3Be C
6～C
12Alkyl.
One type that the present invention designed contains fluorenes, anthracene and benzo two thiophene unit organic semiconductor material, and its preparation scheme is following:
Step S1, following compd A, B, C, D are provided:
Wherein, compd A is 2,7-two bromo-9, and 9-dialkyl group fluorenes, compd B are 9,10-dibromoanthracene or derivatives thereof, Compound C is benzo two thiophene or derivatives thereofs, Compound D is a 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes;
In the formula, R
1, R
2Be respectively hydrogen, fluorine, cyanic acid identical or inequality, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; Preferred R
1, R
2Optional replace or unsubstitutedly have a C
1～C
18Straight chain or branched alkyl or alkoxyl group, optionally replace or show substituted aryl or heteroaryl;
R
3Be C
1～C
20Alkyl, preferred R
3Be C
6～C
12Alkyl;
M is 1～20 integer; Integer between preferred 6≤m≤12;
Step S2: under the anhydrous and oxygen-free reaction conditions, with 2,7-two bromo-9,9-dialkyl group fluorenes (A) and n-Butyl Lithium (n-BuLi) were added in first solvent with mol ratio under-70 ℃～-85 ℃ in 1: 2～1: 4, added 2-isopropoxy-4 then; 4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (D) or two tetramethyl ethylene ketone close two boron; Carry out condensation reaction 12～48 hours, and obtained product, promptly 2,7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes (F); Wherein, first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE; 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two is assorted, and oxygen pentaborane (D) mole dosage are 2,7-two bromo-9,2～4 times of 9-dialkyl group fluorenes (A); The condensation reaction formula is following:
Wherein, first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE; 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two is assorted, and oxygen pentaborane (D) mole dosage are 2,7-two bromo-9,2～4 times of 9-dialkyl group fluorenes (A); 2-isopropoxy-4; 4; 5; 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (D) also can use two tetramethyl ethylene ketones that structural formula is
to close the replacement of two boron;
Step S3: 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 (F), 9; 10-dibromoanthracene or derivatives thereof (B), thieno-[3,4-c] pyrroles-4,6-diketone (C) or derivatives thereof i: j: k in molar ratio adds mixed in second solvent that contains catalyzer and alkali lye; And satisfy i=j+k; Under 70～100 ℃, carry out Suzuki reaction 24～72 hours, obtain the said organic semiconductor material (P) of structural formula for
; The Suzuki reaction formula is following:
In the formula, x, y are real positive value, and x+y=1; The numerical value of x, y is by the feed ratio decision of three kinds of cell cubes;
R
1, R
2Be respectively hydrogen, fluorine, cyanic acid identical or inequality, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; Preferred R
1, R
2Optional replace or unsubstitutedly have a C
1～C
18Straight chain or branched alkyl or alkoxyl group, the optional replacement or unsubstituted aryl or heteroaryl;
R
3Be C
1～C
20Alkyl; Preferred R
3Be C
6～C
12Alkyl;
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, second solvent is toluene, glycol dimethyl ether, THF, ether, methylene dichloride, trichloromethane or ETHYLE ACETATE etc., and catalyst consumption is 2, and 7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.05%～20% of 9-dialkyl group fluorenes molar weight; The mole dosage of alkali is 2 in the alkali lye, and 7-two (4,4,5; 5-tetramethyl--1,3, assorted oxygen pentaboranes of 2-two) base-9,2～20 times of 9-dialkyl group fluorenes (F) molar weight.
Another purpose of the present invention is organic semiconductor material at organic solar batteries, organic electroluminescence device, organic field effect tube, organic optical storage, Application for Field such as organic non-linear device and organic laser apparatus.
The present invention compared with prior art possesses following advantage at least:
1. introduce anthracene and benzo dithienyl group in the organic semiconductor material molecule of the present invention, 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 its carrier mobility improved; Simultaneously; Through modifications such as introducing alkyl in benzo dithienyl group, improved its solvability, thereby improved its processing characteristics;
3. benzo two thiophene is 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 benzo two thiophene units 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; Improved its utilization ratio, simultaneously, made this organic semiconductor material solubility property and charge transport properties excellent sunshine;
4. this organic semiconductor material preparation method technology is simple, and productive rate is high, and reaction conditions is gentle, 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 organic semiconductor material among the present invention as the organic solar batteries device of active coating;
Fig. 2 is with the structural representation of the organic semiconductor material among the present invention as the organic electroluminescence device of luminescent layer;
Fig. 3 is with the structural representation of the organic semiconductor material among the present invention as the organic field effect tube of organic semiconductor layer.
Embodiment
One type provided by the invention contains fluorenes, anthracene and benzo two thiophene unit organic semiconductor material, 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: the integer between 6≤m≤12;
X, y are real positive value, and x+y=1; The numerical value of x, y is by the feed ratio decision 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 the unsubstituted aryl or the heteroaryl of Wasserstoffatoms, fluorine atom, cyanic acid, optional replacement or the unsubstituted 1-18 of having a C atom; Preferred R
1, R
2Be respectively and replace or the unsubstituted C of having
1～C
18Straight chain or branched alkyl or alkoxyl group, the optional replacement or unsubstituted aryl or heteroaryl;
R
3Be C
1～C
20Alkyl; Preferred R
3Be C
6～C
12Alkyl.
Above-mentioned one type to contain fluorenes, anthracene and its preparation scheme of benzo two thiophene unit organic semiconductor material following:
Step S1, following compd A, B, C, D are provided:
Wherein, compd A is 2,7-two bromo-9,9-dialkyl group fluorenes; Compd B is 9,10-dibromoanthracene or derivatives thereof; Compound C is benzo two thiophene or derivatives thereofs; Compound D is a 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes;
In the formula, R
1, R
2Be respectively hydrogen, fluorine, cyanic acid identical or inequality, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; Preferred R
1, R
2Optional replace or unsubstitutedly have a C
1～C
18Straight chain or branched alkyl or alkoxyl group, the optional replacement or unsubstituted aryl or heteroaryl; M is 1～20 integer; The span of preferred m is: the integer between 6≤m≤12;
Step S2: under the anhydrous and oxygen-free reaction conditions, with 2,7-two bromo-9,9-dialkyl group fluorenes (A) and n-Butyl Lithium (n-BuLi) are added in first solvent with mol ratio 1: 2～4 under-70 ℃～-85 ℃, add 2-isopropoxy-4 then; 4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (D) or two tetramethyl ethylene ketone close two boron; Carry out condensation reaction 12～48 hours, and obtained product, promptly 2,7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes (F); Reaction formula is following:
Wherein, 2-isopropoxy-4; 4,5,5-tetramethyl--1; 3,2-two assorted oxygen pentaboranes (D) also can use two tetramethyl ethylene ketones that structural formula is
to close the replacement of two boron; First solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE; 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-two is assorted, and oxygen pentaborane (D) mole dosage are 2,7-two bromo-9,2～4 times of 9-dialkyl group fluorenes (A);
Step S3: 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 (F), 9,10-dibromoanthracene or derivatives thereof (B), benzo two thiophene or derivatives thereof (C) or derivatives thereofs i: j: k in molar ratio add mixed in second solvent that contains catalyzer and alkali lye; And satisfy i=j+k; Under 70～100 ℃, carry out Suzuki reaction 24～72 hours, obtain the said organic semiconductor material (P) of structural formula for
; The Suzuki reaction formula is following:
In the formula, x, y are real positive value, and x+y=1; The numerical value of x, y is by the feed ratio decision of three kinds of cell cubes;
R
1, R
2Be respectively hydrogen, fluorine, cyanic acid identical or inequality, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; Preferred R
1, R
2Optional replace or unsubstitutedly have a C
1～C
18Straight chain or branched alkyl or alkoxyl group, the optional replacement or unsubstituted aryl or heteroaryl;
R
3Be C
1～C
20Alkyl; Preferred R
3Be C
6～C
12Alkyl;
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, second solvent is toluene, glycol dimethyl ether, THF, ether, methylene dichloride, trichloromethane or ETHYLE ACETATE etc., and the mole dosage of catalyzer is 2, and 7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.05%～20% of 9-dialkyl group fluorenes molar weight; The mole dosage of alkali is 2 in the alkali lye, and 7-two (4,4,5; 5-tetramethyl--1,3, assorted oxygen pentaboranes of 2-two) base-9,2～20 times of 9-dialkyl group fluorenes (F) molar weight.
Organic semiconductor material of the present invention is widely used in organic solar batteries, organic electroluminescence device, and organic field effect tube, organic optical storage is in the fields such as organic non-linear device and organic laser apparatus.
Among the present invention, benzo two thiophene simple in structure, its structural formula is as follows:
Atom site relative compact in the molecule, and structure has symmetry, when as the conjugated polymers unit, very strong power supply effect arranged also.Through on phenyl ring, increasing alkane chain, also can increase the solvability and the processibility of conjugated polymers well.At present, benzo two thiophenes have become the active material in the research fields such as organic smooth device.
The present invention has developed a kind of organic semiconductor material that contains fluorenes, anthracene and benzo two thiophene, and is applied to fields such as organic solar batteries.This material has lower energy gap, higher mobility, and the spectrographic absorption region is wide, and this material helps 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 the transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.
Below in conjunction with accompanying drawing, further explain is done in preferred embodiment of the present invention.
Embodiment 1
Open following organic semiconductor material polymer P 1, the P2 of structure of present embodiment:
The preparation process of P1, P2 is following:
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:
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 150ml purified tetrahydrofuran solvent with syringe, under-78 ℃ of conditions, slowly injects 27.0mmol n-BuLi with syringe again, 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.
Behind the reaction knot table, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and steam solvent.At last crude product is used sherwood oil: ETHYLE ACETATE (v/v=15: 1) separate, 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% for leacheate carries out silica gel column chromatography.GC-MS(EI-m/z)：642(M
+)。
The preparation of step 2, P1, P2:
In reactor drum, 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, 2,6-two bromo-4,8-two (hexyloxy) benzo two thiophene 0.9mmol, tetra-triphenylphosphine palladium (Pd (PPh
3)
4) Na of 0.025mmol, 2mol/L
2CO
3Aqueous solution 5ml and toluene solvant 30ml are through lead 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 used dissolved in chloroform, cross chromatography column, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash in the methanol solvate it and stirred for several hour, at last polymer P 1 is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph; The 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 GPC test, number-average molecular weight Mn ≈ 75600; The polymkeric substance monodispersity is 1.36, and n is 100.
In reactor drum, 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, 2,6-two bromo-4; 8-two (hexyloxy) benzo two thiophene 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 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 GPC test, number-average molecular weight Mn ≈ 43600; The polymkeric substance monodispersity is 1.59, and n is 65.
Embodiment 2
Open following organic semiconductor material polymer P 3, the P4 of structure of present embodiment:
The preparation process of P3, P4 is following:
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 implementation example 1.
The preparation of step 3, P3, P4:
In reactor drum, 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.2006,207 for 6-two (2-octyl-decyl) anthracene 0.8mmol; 1107-1115), 2,6-two bromo-4,8-two (octyloxy) benzo two thiophene 0.2mmol, palladium (Pd (OAc)
2) Na of 3mg, 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 40ml are through lead to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 100 ℃ of conditions, react 24h.
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 used dissolved in chloroform, cross chromatography column, remove catalyzer, at last polymkeric substance/chloroform is dissolved to revolve and steam to the surplus 5ml, splash in the methanol solvate it and stirred for several hour, at last polymer P 3 is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph; The 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 GPC test, number-average molecular weight Mn ≈ 36700; The polymkeric substance monodispersity is 1.97, and n is 38.
In reactor drum, 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, 2,6-two bromo-4; 8-two (octyloxy) benzo two thiophene 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 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 GPC test, number-average molecular weight Mn ≈ 35500; The polymkeric substance monodispersity is 2.13, and n is 43.
Embodiment 3
Open following organic semiconductor material polymer P 5, the P6 of structure of present embodiment:
The preparation process of P5, P6 is following:
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 implementation example 1.
The preparation of step 2, P5, P6:
In reactor drum, add 2,7-two (4,4,5; 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-two (dodecyl) fluorenes 1mmol, 9; (compound method of this compound is referring to people's such as Elimelech Rochlin J.Org.Chem., 2003,68 for 10-two bromo-2-fluorine anthracene 0.5mmol; 216-226), 2,6-two bromo-4,8-two (2-ethylhexyl oxygen base) benzo two thiophene 0.5mmol, tetra-triphenylphosphine palladium (Pd (PPh
3)
4) Na of 0.02mmol, 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 40ml are through lead to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 80 ℃ of conditions, react 58h.
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 the solid powder is used dissolved in chloroform, cross chromatography column, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash in the methanol solvate it and stirred for several hour, at last polymer P 5 is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph; The 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 GPC test, number-average molecular weight Mn ≈ 20500; The polymkeric substance monodispersity is 2.11, and n is 25.
In reactor drum, 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, 2,6-two bromo-4; 8-two (2-ethylhexyl oxygen base) benzo two thiophene 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 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 GPC test, number-average molecular weight Mn ≈ 21500; The polymkeric substance monodispersity is 2.54, and n is 27.
Embodiment 4
Open following organic semiconductor material polymer P 7, the P8 of structure of present embodiment:
The preparation process of P7, P8 is following:
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 implementation example 1.
The preparation of step 2, P7, P8:
In reactor drum, 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, (compound 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), 2,6-two bromo-4, the Na of 8-two (dodecyloxy) benzo two thiophene 0.5mmol, tricyclohexyl phosphine 5mg, 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 50ml are through lead 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 the solid powder is used dissolved in chloroform, cross chromatography column, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last,, at last polymer P 7 is collected oven dry in its eight methanol solvate and stirred for several hour with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph; The 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 GPC test, number-average molecular weight Mn ≈ 61400; The polymkeric substance monodispersity is 1.41, and n is 73.
In reactor drum, 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, 2,6-two bromo-4; 8-two (dodecyloxy) benzo two thiophene 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 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 GPC test, number-average molecular weight Mn ≈ 52400; The polymkeric substance monodispersity is 1.61, and n is 60.
The present invention also provides a class formation formula to do
Contain fluorenes, anthracene and benzo two thiophene unit organic semiconductor material at organic solar batteries, organic electroluminescent, organic field effect tube, organic optical storage, Application for Field such as organic non-linear device and organic laser apparatus; 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; The numerical value of x, y is by the feed ratio decision of three kinds of cell cubes; R
1, R
2Be respectively hydrogen, fluorine, cyanic acid identical or inequality, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; R
3Be C
1～C
20Alkyl.
Following examples are one type and contain fluorenes, anthracene and benzo two thiophene unit organic semiconductor material at organic solar batteries, organic field effect tube, the application in the organic electroluminescence device.
Embodiment 5
With the organic solar batteries device of the P1 among the embodiment 1 as active layer material
A kind of organic solar batteries device, its structure is 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 a mixture, comprises electron donor material, and PCBM is an electron acceptor material; Electron donor material is a material with the P1 among the embodiment 1, 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 for gathering (3, the 4-Ethylenedioxy Thiophene), and PSS is for gathering (styrene sulfonic acid); Preferred square resistance is the ITO of 10 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 as the anodic conductive layer, and thickness is about 50-300nm;
Ito glass is through ultrasonic cleaning, and with after oxygen-Plasma processing, plays the PEDOT:PSS layer 13 of modification at ITO surfaces coated last layer, and thickness is 50-300nm;
The employing spin coating technique applies layer of active layer 14 on (styrene sulfonic acid) layer in order to gather gathering (3, the 4-Ethylenedioxy Thiophene): PSS, and 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 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 100 ℃ of air tight conditions annealing 3 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved the 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 6
With the P1 among the embodiment 1 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 impact plies 24/Al layer 25; Wherein: luminescent layer is a material with the P1 among the embodiment 1.
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 as the anodic conductive layer, and thickness is 50-300nm; Preferred square resistance is the ITO of 10 Ω/mouths.
Is the luminescent layer 23 of material at ITO surface preparation one deck with the P1 among the embodiment one through spin coating technique, and thickness is about 50-300nm;
Vacuum evaporation LiF on luminescent layer, as impact plies 14, thickness is about 0.3-2nm;
Vacuum evaporation metallic aluminium on said luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains said organic electroluminescence device.
Embodiment 7
P1 to contain among the embodiment 1 is the organic field effect tube of material
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 31/500nm is thick
2Insulation layer 32/ is used to modify 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 a 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, on a surface cleaning doped silicon wafer 31, apply one deck SiO later
2 Insulation layer 32; Secondly, at said 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 said octadecyl trichlorosilane layer, and thickness is about 50-300nm; At last, on said 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 a material, obtain said organic field effect tube.
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. one type of formula (P) contains fluorenes, anthracene and benzo two thiophene unit organic semiconductor material:
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, cyanic acid, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; R
3Be C
1～C
20Alkyl.
2. one type of organic semiconductor material that contains fluorenes, anthracene and benzo two thiophene units according to claim 1 is characterized in that the span of said m is: the integer between 6≤m≤12; Said R
1, R
2Be respectively and have C
1～C
40Straight or branched alkyl, have C
1～C
18The alkoxyl group of straight or branched; Said R
3Be C
6～C
12Alkyl.
3. one type of preparation method who contains fluorenes, anthracene and benzo two thiophene unit organic semiconductor material is characterized in that, comprises the steps:
Step S1, following compd A, B, C, D are provided:
In the formula, R
1, R
2Respectively hydrogen, fluorine, cyanic acid, have C
1～C
40Straight or branched alkyl, have C
1～C
40Alkoxyl group, aryl or the heteroaryl of straight or branched; R
3Be C
1～C
20Alkyl; M is 1～20 integer;
Step S2, in oxygen-free environment; With compound (A) and n-Butyl Lithium under-70 ℃～-85 ℃; Be added in first solvent in 1: 2～1: 4 with mol ratio; Adding molar weight then is the compound (D) of 2～4 times of compound (A) molar weights; Reacted 12～48 hours, and obtained the compound (F) of structural formula for
;
In step S3, the oxygen-free environment; With the compound (B) among compound that makes among the step S2 (F) and the step S1, compound (C) in molar ratio i: j: k add in second solvent contain catalyzer and alkali lye and mix; Under 70～100 ℃, carry out Suzuki reaction 24～72 hours, obtain the said class of structural formula and contain fluorenes, anthracene and benzo two thiophene unit organic semiconductor material (P) for
; In the formula, n is 1～200 integer; Wherein, i=j+k, x, y are arithmetic number, and x+y=1.
4. preparation method according to claim 3 is characterized in that, the span of said m is: the integer between 6≤m≤12; Said R
1, R
2Be respectively and have C
1～C
40Straight or branched alkyl, have C
1～C
18The alkoxyl group of straight or branched; Said R
3Be C
6～C
12Alkyl.
5. preparation method according to claim 3 is characterized in that, said first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE.
6. preparation method according to claim 3 is characterized in that, the mole dosage of said catalyzer is 0.05%～20% of compound (F) molar weight; Said catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand.
7. preparation method according to claim 6 is characterized in that, said organic palladium is Pd (PPh
3)
4, Pd (OAc)
2, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2Said organophosphor ligand is tricyclohexyl phosphine or P (o-Tol)
3
8. preparation method according to claim 6 is characterized in that, said alkali lye is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; The mole dosage of alkali is 2～20 times of compound F 17-hydroxy-corticosterone molar weight in the said alkali lye.
9. preparation method according to claim 3 is characterized in that, said second solvent is at least a in toluene, glycol dimethyl ether, THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE.
10. one type of organic semiconductor material that contains fluorenes, anthracene and benzo two thiophene units as claimed in claim 1 is at organic solar batteries; Organic electroluminescence device; Organic field effect tube, organic optical storage, Application for Field such as organic non-linear device and organic laser apparatus.
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Cited By (5)
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| CN103664994A (en) * | 2012-08-31 | 2014-03-26 | 昆山维信诺显示技术有限公司 | Benzodithiophene derivative organic electroluminescent material and application thereof |
| CN103865041A (en) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof |
| CN104629004A (en) * | 2013-11-13 | 2015-05-20 | 北京师范大学 | 9-arylene-9H-fluorene based donor-acceptor alternating copolymer, preparation method thereof and application in organic optoelectronic devices |
| CN110818910A (en) * | 2019-11-13 | 2020-02-21 | 北京大学深圳研究生院 | N-type polymer thermoelectric material |
| CN113345919A (en) * | 2021-05-25 | 2021-09-03 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
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| US20070270595A1 (en) * | 2006-05-22 | 2007-11-22 | Myeong-Suk Kim | Organic light-emitting compound and organic electroluminescent device using the same |
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| CN1840525A (en) * | 2005-12-31 | 2006-10-04 | 清华大学 | Organic electroluminescent material and its application |
| US20070270595A1 (en) * | 2006-05-22 | 2007-11-22 | Myeong-Suk Kim | Organic light-emitting compound and organic electroluminescent device using the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664994A (en) * | 2012-08-31 | 2014-03-26 | 昆山维信诺显示技术有限公司 | Benzodithiophene derivative organic electroluminescent material and application thereof |
| CN103865041A (en) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof |
| CN103865041B (en) * | 2012-12-12 | 2016-02-10 | 海洋王照明科技股份有限公司 | Containing the conjugated polymers and its preparation method and application of bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene |
| CN104629004A (en) * | 2013-11-13 | 2015-05-20 | 北京师范大学 | 9-arylene-9H-fluorene based donor-acceptor alternating copolymer, preparation method thereof and application in organic optoelectronic devices |
| CN110818910A (en) * | 2019-11-13 | 2020-02-21 | 北京大学深圳研究生院 | N-type polymer thermoelectric material |
| CN113345919A (en) * | 2021-05-25 | 2021-09-03 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
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