CN103626969A - Copolymer containing perylenetetracarboxylic diimide-s-indacenobithiophene, preparation method thereof and applications thereof - Google Patents
Copolymer containing perylenetetracarboxylic diimide-s-indacenobithiophene, preparation method thereof and applications thereof Download PDFInfo
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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Abstract
The invention belongs to the field of organic semiconductor materials, and discloses a copolymer containing perylenetetracarboxylic diimide-s-indacenobithiophene, a preparation method thereof and applications thereof. The copolymer has a general structure formula as follows, wherein n is an integer between 1 and 100; R1, R2 and R3 are the same or different and are selected from hydrogen, C1-C20 alkyl or C1-C20 alkoxy; and R4 is C1-C20 alkyl or C1-C20 alkylbenzene. According to the copolymer, the s-indacenobithiophene unit and the perylenetetracarboxylic diimide are subjected to copolymerization to form an electron donor-receptor structure so as to adjust the bad gap of the polymer and to push the absorption band edge of the polymer to infrared and near infrared zones, thus increasing the sunlight utilization rate and further increasing the light conversion rate.
Description
Technical field
The present invention relates to organic semiconductor material, relate in particular to multipolymer of a kind of Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene and its preparation method and application.
Background technology
Utilize cheap material preparation low cost, dynamical organic semiconductor device, as, organic solar batteries, organic electroluminescence device, organic field effect tube are study hotspot and the difficult points in photovoltaic field always.The current silicon solar cell for ground, because complex manufacturing, cost are high, is restricted its application.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Organic semiconductor device receives much concern because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage, if its energy conversion efficiency can be brought up to the level that approaches commodity silicon solar cell, its market outlook will be very huge.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C
60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect organic semiconductor device, and have obtained development at full speed.At present, the research of organic solar batteries mainly concentrates on to body, acceptor co-mixing system, adopts PTB7 and PC
71the energy conversion efficiency of BM co-mixing system has reached 7.4%(Y.Liang et al., Adv.Mater.; DOI:10.1002/adma.200903528), but still much lower than the efficiency of conversion of inorganic solar cell, the main restricting factor that limiting performance improves has: the carrier mobility that organic semiconductor device is relatively low, the spectral response of device is not mated with solar radiation spectrum, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.For organic semiconductor device is on the actual application, the material of development of new, increases substantially the top priority that its effciency of energy transfer is still this research field.
Perylene tetracarboxylic acid diimides and derivative thereof have large common phenyl ring two dimensional structure and two imide ring structures, in visible region, there is very strong absorption, there is higher light, heat and environmental stability, there is higher electron affinity (lower lumo energy), and because stacking the making of π-π between the large π key of its conjugation has very high electronic mobility along stacking direction, therefore, it all shows wide application prospect at multiple fields such as organic photovoltaic cells.But You Yu perylene tetracarboxylic acid diimides and derivative thereof contain large planar conjugate system and good molecule coplanarity, the interaction of intermolecular large π key is very strong, there is larger lattice energy, thereby its solvability is poor, film forming processing characteristics is poor, causes the device of preparation to be easy to occur problem of phase separation, affect the efficiency of exciton diffusion, thereby cause the loss of energy.The absorption spectrum of You Yu perylene tetracarboxylic acid diimides and derivative thereof mainly concentrates on visible region in addition, and absorption region is wide not enough, high not enough with the emmission spectrum matching degree of sunlight, can not effectively utilize sunlight, also can reduce the photoelectric transformation efficiency of organic semiconductor device.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of multipolymer that can improve organic semiconductor device photoelectric transformation efficiency Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene.
Technical scheme of the present invention is as follows:
A multipolymer for Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, has following general structure:
In formula: n is the integer between 1-100; R
1, R
2, R
3be hydrogen, C identical or differently
1~ C
20alkyl or C
1~ C
20alkoxyl group; R
4for C
1~ C
20alkyl or C
1~ C
20alkylbenzene.
Described multipolymer, wherein, preferably n is the integer between 12-56.
The preparation method who the invention provides the multipolymer of above-mentioned Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, comprises the steps:
Under inert atmosphere, by structural formula, be
compd A and structural formula be
compd B according to the ratio of mol ratio 1:1 ~ 1:1.2, add in the solvent that catalyzer exists, at 50 ~ 120 ℃, carry out Stille coupling reaction 24 ~ 72 hours, stopped reaction, makes structural formula and is
the multipolymer of Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene;
In above-mentioned formula, n is the integer between 1-100; R
1, R
2, R
3be hydrogen, C identical or differently
1~ C
20alkyl or C
1~ C
20alkoxyl group; R
4for C
1~ C
20alkyl or C
1~ C
20alkylbenzene.
Described preparation method, wherein, preferably n is the integer between 12-56.
Described preparation method, wherein, after Stille coupling reaction finishes, also comprises described multipolymer is carried out to purification process process:
In the reaction solution that Stille coupling reaction is obtained, add in methyl alcohol and carry out sedimentation, suction filtration, washing, dry, obtain dry thing;
With toluene, dissolve dry thing, obtain solution, subsequently liquid is joined in the aqueous solution of Thiocarb, obtain mixing solutions; Then mixed solution is heated to 90 ℃ of stirrings and spends the night, obtain organic phase and the inorganic phase of layering;
By organic phase, by chromatography, drip washing, decompression are removed organic solvent, and again through sedimentation, suction filtration, are obtained screening; And extract screening by acetone Soxhlet, and then to the screening sedimentation of extracting, suction filtration, takes out and spends the night under vacuum pump, obtains the described multipolymer of purifying.
Described preparation method, wherein, described catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
Described preparation method, wherein, described catalyzer is that mol ratio is three (dibenzalacetone) two palladiums of 1:2 ~ 20 and the mixture of three (o-methyl-phenyl-) phosphine; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
Described preparation method, wherein, described solvent is tetrahydrofuran (THF), dioxane, N, at least one in N-dimethyl amide, benzene and toluene.
The present invention also provides the application of above-mentioned multipolymer in organic solar batteries, organic electroluminescence device, organic field effect tube.
The multipolymer of Han perylene tetracarboxylic acid diimides provided by the invention-symmetrical indacene 1,4-Dithiapentalene, the one, by introducing substituting group in its " bay " position, the 2nd, Tong Guo perylene tetracarboxylic acid diimides monomer and other monomer copolymerizations, improve its solvability.In addition, 1,4-Dithiapentalene unit, symmetrical indacene is the unit with good two dimensional structure that simultaneously contains two five yuan of thiphene ring and one " s-indacene " symmetrical indacene ring skeleton, due to its good planeness and conjugation degree, its hole mobility is very high, and 4 in the 1,4-Dithiapentalene of symmetrical indacene, can introduce the modifications such as alkyl for 9 and improve its solvability, and improve its solution processable performance.Therefore, symmetrical indacene 1,4-Dithiapentalene Dan, Yu perylene tetracarboxylic acid diimides copolymerization forms Electron donor acceptor structure, carrys out the band gap of telomerized polymer, and pushes its energy of absorption edge to infrared and near-infrared region.The solvability of modifying Hou perylene tetracarboxylic acid diimides is good, and absorbancy is strong, and absorption region is wide, may extend to near-infrared region, improved its utilization ratio to sunlight, and then improve light turnover ratio, there is good charge transport properties, in the fields such as organic photovoltaic cell, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic solar batteries that makes of embodiment 7;
Fig. 2 is the structural representation of the organic electroluminescence device that makes of embodiment 8;
Fig. 3 is the structural representation of the organic field effect tube that makes of embodiment 9.
Embodiment
The multipolymer of a kind of Han perylene tetracarboxylic acid diimides-symmetrical indacene provided by the invention 1,4-Dithiapentalene, has following general structure:
In formula: n is the integer between 1-100, preferably n is the integer between 12-56; R
1, R
2, R
3be hydrogen, C identical or differently
1~ C
20alkyl or C
1~ C
20alkoxyl group; R
4for C
1~ C
20alkyl or C
1~ C
20alkylbenzene.
The preparation method of the multipolymer of above-mentioned Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, comprises the steps:
Under S1, inert atmosphere (comprising that nitrogen, argon gas or nitrogen and argon gas form the inert atmosphere that mixed gas forms), by structural formula, be
compd A (perylene tetracarboxylic acid diimides two bromo-derivatives) and structural formula be
compd B (2, two tributyl tin-symmetrical the indacene of 7-1,4-Dithiapentalene derivative) according to the ratio of mol ratio 1:1 ~ 1:1.2, add in the solvent that catalyzer exists, at 50 ~ 120 ℃, carry out Stille coupling reaction 24 ~ 72 hours, stopped reaction, makes and contains structural formula and be
the reaction solution of the multipolymer of Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene; Above-mentioned various in: n is the integer between 1-100; R
1, R
2, R
3be hydrogen, C identical or differently
1~ C
20alkyl or C
1~ C
20alkoxyl group; R
4for C
1~ C
20alkyl or C
1~ C
20alkylbenzene; Reaction formula is as follows:
After S2, Stille coupling reaction finish, to making multipolymer in step S1, carry out purification process process:
Reaction solution is added drop-wise in methyl alcohol and carries out sedimentation, suction filtration, methanol wash, dry; Then with toluene, dissolve, join in the aqueous solution of Thiocarb; Then mixed solution is heated to 90 ℃ of stirrings and spends the night, by organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing; Organic solvent, methyl alcohol sedimentation are removed in decompression; Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the multipolymer of purifying.
In above-mentioned preparation method, described catalyzer is tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) or two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2); Or described catalyzer is that mol ratio is three (dibenzalacetone) two palladium (Pd of 1:2 ~ 20
2(dba)
3) and three (o-methyl-phenyl-) phosphine (P (o-tol)
3) mixture; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
In above-mentioned preparation method, described solvent is tetrahydrofuran (THF) (THF), dioxane, N, at least one in N-dimethyl amide (DMF), benzene and toluene.
The present invention also provides the application of above-mentioned multipolymer in organic solar batteries, organic electroluminescence device, organic field effect tube.
The multipolymer of Han perylene tetracarboxylic acid diimides provided by the invention-symmetrical indacene 1,4-Dithiapentalene, the one, by introducing substituting group in its " bay " position, the 2nd, Tong Guo perylene tetracarboxylic acid diimides monomer and other monomer copolymerizations, improve its solvability.In addition, 1,4-Dithiapentalene unit, symmetrical indacene is the unit with good two dimensional structure that simultaneously contains two five yuan of thiphene ring and one " s-indacene " symmetrical indacene ring skeleton, due to its good planeness and conjugation degree, its hole mobility is very high, and 4 in the 1,4-Dithiapentalene of symmetrical indacene, can introduce the modifications such as alkyl for 9 and improve its solvability, and improve its solution processable performance.Therefore, symmetrical indacene 1,4-Dithiapentalene Dan, Yu perylene tetracarboxylic acid diimides copolymerization forms Electron donor acceptor structure, carrys out the band gap of telomerized polymer, and pushes its energy of absorption edge to infrared and near-infrared region.The solvability of modifying Hou perylene tetracarboxylic acid diimides is good, and absorbancy is strong, and absorption region is wide, may extend to near-infrared region, improved its utilization ratio to sunlight, and then improve light turnover ratio, there is good charge transport properties, in the fields such as organic photovoltaic cell, have a good application prospect.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The multipolymer of the present embodiment Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, gathers N, N '-bis--(3,4,5-tri--dodecyloxy benzene)-3,4,9,10-perylene diimides-4, the symmetrical indacene of 4,9,9-tetra-(dodecyl) also [3,2-b:7,6-b '] two thiophene (n=56):
Under nitrogen protection, toward containing compound N, N '-bis--(3; 4,5-, tri--dodecyloxy benzene)-1,7-bis-bromo-3; 4,9,10-perylene diimides 0.5mmol; two tributyl tin-4 of 2,7-, 4; 9; dissolve the symmetrical indacene of 9-tetra-(dodecyl) the also DMF solvent (18mL) of [3,2-b:7,6-b '] two thiophene 0.5mmol.Continue to pass into nitrogen bubble 0.5h and remove residual oxygen.Then add Pd
2(dba)
3(0.0.14g, 0.015mol) and P (o-Tol)
3(0.0083g, 0.027mmol), again continues to pass into nitrogen bubble 0.5h and removes residual oxygen, is then heated to 80 ℃ and carries out Stille coupling reaction 48 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(3,4,5-, tri--dodecyloxy benzene)-3,4,9, and 10-perylene diimides-4, the symmetrical indacene of 4,9,9-tetra-(dodecyl) is [3,2-b:7,6-b '] two thiophene also.Molecular?weight(GPC,THF,R.I):M
n=146,700,M
w/M
n=3.32.
Embodiment 2
The multipolymer of the present embodiment Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, gather N, N '-bis--(4-eicosyl-3,5-dimethoxy benzene)-3,4,9,10-perylene diimides-4,4,9, the symmetrical indacene of 9-tetra-(eicosyl) is [3,2-b:7,6-b '] two thiophene (n=43) also:
Under nitrogen protection, toward containing compound N N, N '-bis--(4-eicosyl-3; 5-dimethoxy benzene)-1,7-bis-bromo-3,4; 9,10-perylene diimides 0.5mmol, 2; two tributyl tin-4 of 7-; the symmetrical indacene of 4,9,9-tetra-(eicosyl) also [3; 2-b:7,6-b '] the dioxane solvent (15mL) of two thiophene 0.5mmol dissolves.Continue to pass into nitrogen bubble 0.5h and remove residual oxygen.Then add Pd (PPh
3)
2cl
2(10mg, 0.014mmol), again continues to pass into nitrogen bubble 0.5h and removes residual oxygen, is then heated to 120 ℃ and carries out Stille coupling reaction 24 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(4-eicosyl-3,5-dimethoxy benzene)-3,4,9, and 10-perylene diimides-4, the symmetrical indacene of 4,9,9-tetra-(eicosyl) is [3,2-b:7,6-b '] two thiophene also.Molecular?weight(GPC,THF,R.I):M
n=112,700,M
w/M
n=2.79。
Embodiment 3
The multipolymer of the present embodiment Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, gather N, N '-bis--(3,5-dioctyl-4-eicosane oxygen base) benzene-3,4,9,10-perylene diimides-4,4,9,9-tetra-octyl groups-symmetrical indacene is [3,2-b:7,6-b '] two thiophene (n=41) also:
Under argon shield, toward containing compound N, N '-bis--(3; 5-dioctyl-4-eicosane oxygen base) benzene-1,7-bis-bromo-3,4; 9,10-perylene diimides 0.5mmol, 2; two tributyl tin-4 of 7-; 4,9,9-, tetra-octyl groups-symmetrical indacene also [3; 2-b:7,6-b '] toluene and the THF mixed solvent (30mL) of two thiophene 0.5mmol dissolve.Continue to pass into argon gas bubbling 0.5h and remove residual oxygen.Then add Pd (PPh
3)
4(8mg, 0.011mmol), again passes into argon gas bubbling 0.5h and removes residual oxygen, is then heated to 50 ℃ and carries out Stille coupling reaction 72 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(3,5-dioctyl-4-eicosane oxygen base) benzene-3, and 4,9,10-perylene diimides-4,4,9,9-, tetra-octyl groups-symmetrical indacene is [3,2-b:7,6-b '] two thiophene also.Molecular?weight(GPC,THF,R.I):M
n=94,720,M
w/M
n=2.86。
Embodiment 4
The multipolymer of the present embodiment Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, be N, N '-bis--(4-methoxyl group-3,5-bis--eicosane oxygen base) benzene-3,4,9,10-perylene diimides-4,4,9,9-tetra-hexyls-symmetrical indacene is [3,2-b:7,6-b '] two thiophene (n=38) also:
Under nitrogen protection, toward containing compound N, N '-bis--(4-methoxyl group-3; 5-bis--eicosane oxygen base) benzene-1,7-bis-bromo-3,4; 9,10-perylene diimides 0.52mmol, 2; two tributyl tin-4 of 7-; 4,9,9-, tetra-hexyls-symmetrical indacene also [3; 2-b:7,6-b '] benzene solvent (20mL) of two thiophene 0.5mmol dissolves.Continue to pass into nitrogen bubble 0.5h and remove residual oxygen.Then add Pd (PPh
3)
2cl
2(5mg, 0.007mmol), again continues to pass into nitrogen bubble 0.5h and removes residual oxygen, is then heated to 100 ℃ and carries out Stille coupling reaction 56 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(4-methoxyl group-3,5-bis--eicosane oxygen base) benzene-3, and 4,9,10-perylene diimides-4,4,9,9-, tetra-hexyls-symmetrical indacene is [3,2-b:7,6-b '] two thiophene also.Molecular?weight(GPC,THF,R.I):M
n=91,530,M
w/M
n=3.23。
Embodiment 5
The multipolymer of the present embodiment Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, gathers N, N '-bis--(3-eicosane oxygen base benzene)-3,4,9,10-perylene diimides-4,4,9,9-tetramethyl--symmetrical indacene is [3,2-b:7,6-b '] two thiophene (n=12) also:
Under nitrogen protection, toward containing compound N, N '-bis--((3-eicosane oxygen base benzene)-1; 7-bis-bromo-3,4,9; 10-perylene diimides 0.51mmol; two tributyl tin-4 of 2,7-, 4; 9; dissolve 9-tetramethyl--symmetrical indacene also toluene and the DMF mixed solvent (25mL) of [3,2-b:7,6-b '] two thiophene 0.6mmol.Continue to pass into nitrogen bubble 0.5h and remove residual oxygen.Then add Pd (PPh
3)
4(10mg, 0.014mmol), again continues to pass into nitrogen bubble 0.5h and removes residual oxygen, is then heated to 70 ℃ and carries out Stille coupling reaction 40 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(3-eicosane oxygen base benzene)-3,4,9, and 10-perylene diimides-4,4,9,9-tetramethyl--symmetrical indacene is [3,2-b:7,6-b '] two thiophene also.Molecular?weight(GPC,THF,R.I):M
n=17,580,M
w/M
n=2.69。
Embodiment 6
The multipolymer of the present embodiment Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, gathers N, N '-bis--(3,4,5-tri--eicosane oxygen base benzene)-3,4,9,10-perylene diimides-4, tetra-pairs of hexyl benzene-title indacene of 4,9,9-also [3,2-b:7,6-b '] two thiophene (n=29):
Under nitrogen and the protection of argon gas gas mixture, toward containing compound N, N '-bis--(3; 4,5-, tri--eicosane oxygen base benzene)-1,7-bis-bromo-3; 4,9,10-perylene diimides 0.75mmol; two tributyl tin-4 of 2,7-, 4; 9; dissolve 9-tetra-pairs of hexyl benzenes-symmetrical indacene also dioxane and the THF mixed solvent (18mL) of [3,2-b:7,6-b '] two thiophene 0.5mmol.Continue to pass into nitrogen and argon gas gas mixture bubbling 0.5h removes residual oxygen.Then add Pd (PPh
3)
2cl
2(8mg, 0.011mmol), continues to pass into nitrogen again and argon gas gas mixture bubbling 0.5h removes residual oxygen, is then heated to 65 ℃ and carries out Stille coupling reaction 72 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(3,4,5-, tri--eicosane oxygen base benzene)-3,4,9, and 10-perylene diimides-4, tetra-pairs of hexyl benzene-title indacene of 4,9,9-are [3,2-b:7,6-b '] two thiophene also.Molecular?weight(GPC,THF,R.I):M
n=94,400,M
w/M
n=2.69。
Embodiment 7
The present embodiment is organic solar batteries device, and it gather N with the multipolymer in embodiment 1, N '-bis--(3,4,5-, tri--dodecyloxy benzene)-3,4,9,10-perylene diimides-4,4,9, the symmetrical indacene of 9-tetra-(dodecyl) also [3,2-b:7,6-b '] two thiophene (being expressed as P1) as the material of active coating.
An 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; The P1 that electron donor material be take in embodiment 1 is material, 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); Preferably square resistance is the ITO of 10 Ω/mouths.
The preparation process of this organic solar batteries device is:
Tin indium oxide (ITO) layer 12 that is 10-20 Ω/mouth at surface deposition one deck square resistance of glass substrate 11, forms the conductive layer as anode, and thickness is about 50-300nm;
Ito glass process ultrasonic cleaning, and after processing with oxygen-Plasma, on ITO surface, be coated with the PEDOT:PSS layer 13 that last layer plays modification, thickness is 50-300nm;
At poly-(3,4-Ethylenedioxy Thiophene): PSS, for gathering on (styrene sulfonic acid) layer, adopt spin coating technique to apply one deck active coating 14, thickness is 50-300nm, and the material of this active coating 14 is with the P1 in embodiment 1 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 organic solar batteries device;
Organic solar batteries device, with after epoxy encapsulation, is placed under 100 ℃ of air tight conditions and is annealed 3 hours, then drop to room temperature.Due to device annealed after, the chemical structure of material is more regular in order, has improved transmission speed and the efficiency of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Preferably the thickness of ITO, PEDOT:PSS layer, active coating, Al layer is respectively 150nm, 50nm, 120nm, 100nm.
Embodiment 8
The present embodiment is organic electroluminescence device, and it gather N with the multipolymer in embodiment 2, N '-bis--(4-eicosyl-3,5-dimethoxy benzene)-3,4,9,10-perylene diimides-4, the symmetrical indacene of 4,9,9-tetra-(eicosyl) also [3,2-b:7,6-b '] two thiophene (being expressed as P2) are as the material of luminescent layer.
An 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: the P2 that luminescent layer 23 be take in embodiment 2 is material.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) layer 22 that is 10-20 Ω/mouth at surface deposition one deck square resistance of glass substrate 21, forms the conductive layer as anode, and thickness is 50-300nm; Preferably square resistance is the ITO of 10 Ω/mouths.
The luminescent layer 23 that to prepare P2 that one deck take in embodiment 2 be material on ITO surface 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.The output of accompanying drawing 1, represents that this polymkeric substance produces photoelectric current as the organic solar batteries of active coating under illumination effect, realizes opto-electronic conversion.
Embodiment 9
The present embodiment is organic field effect tube, and it gather N with the multipolymer containing in embodiment 3, N '-bis--(3,5-dioctyl-4-eicosane oxygen base) benzene-3,4,9,10-perylene diimides-4,4,9,9-, tetra-octyl groups-symmetrical indacene also [3,2-b:7,6-b '] two thiophene (being expressed as P3) are as the material of organic semiconductor layer.
An 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 Si31/450nm is thick
2insulation layer 32/ is for modifying SiO
2octadecyl trichlorosilane alkane (OTS) layer 33/ organic semiconductor layer 34/ take source electrode (S) 35 and the drain electrode (D) 36 that gold is material; Wherein, the P3 that organic semiconductor layer 34 be take in embodiment 3 is material; Wherein, source electrode (S) and drain electrode (D) material also can be selected copper material.
The preparation process of this organic field effect tube is:
First, on a surface cleaning doped silicon wafer 31 later, apply one deck SiO
2insulation layer 32; Secondly, at described SiO
2on insulation layer, apply the octadecyl trichlorosilane alkane layer 33 that one deck plays modification, thickness is 10-200nm; Then, the organic semiconductor layer 34 that the P1 that spin coating one deck be take in embodiment mono-on described octadecyl trichlorosilane alkane layer is material, thickness is about 50-300nm; Finally, on described organic semiconductor layer, be arranged at intervals with and take 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, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. containing a multipolymer for perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, it is characterized in that, this multipolymer has following general structure:
In formula: n is the integer between 1-100; R
1, R
2, R
3be hydrogen, C identical or differently
1~ C
20alkyl or C
1~ C
20alkoxyl group; R
4for C
1~ C
20alkyl or C
1~ C
20alkylbenzene.
2. multipolymer according to claim 1, is characterized in that, n is the integer between 12-56.
3. contain a preparation method for the multipolymer of perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene, it is characterized in that, comprise the steps:
Under inert atmosphere, by structural formula, be
compd A and structural formula be
compd B according to the ratio of mol ratio 1:1 ~ 1:1.2, add in the solvent that catalyzer exists, at 50 ~ 120 ℃, carry out Stille coupling reaction 24 ~ 72 hours, stopped reaction, makes structural formula and is
the multipolymer of Han perylene tetracarboxylic acid diimides-symmetrical indacene 1,4-Dithiapentalene;
In above-mentioned formula, n is the integer between 1-100; R
1, R
2, R
3be hydrogen, C identical or differently
1~ C
20alkyl or C
1~ C
20alkoxyl group; R
4for C
1~ C
20alkyl or C
1~ C
20alkylbenzene.
4. preparation method according to claim 3, is characterized in that, n is the integer between 12-56.
5. preparation method according to claim 3, is characterized in that, after Stille coupling reaction finishes, also comprises described multipolymer is carried out to purification process process:
In the reaction solution that Stille coupling reaction is obtained, add in methyl alcohol and carry out sedimentation, suction filtration, washing, dry, obtain dry thing;
With toluene, dissolve dry thing, obtain solution, subsequently liquid is joined in the aqueous solution of Thiocarb, obtain mixing solutions; Then mixed solution is heated to 90 ℃ of stirrings and spends the night, obtain organic phase and the inorganic phase of layering;
By organic phase, by chromatography, drip washing, decompression are removed organic solvent, and again through sedimentation, suction filtration, are obtained screening; And extract screening by acetone Soxhlet, and then to the screening sedimentation of extracting, suction filtration, takes out and spends the night under vacuum pump, obtains the described multipolymer of purifying.
6. preparation method according to claim 3, is characterized in that, described catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
7. preparation method according to claim 3, is characterized in that, described catalyzer is that mol ratio is three (dibenzalacetone) two palladiums of 1:2 ~ 20 and the mixture of three (o-methyl-phenyl-) phosphine; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
8. preparation method according to claim 3, is characterized in that, described solvent is tetrahydrofuran (THF), dioxane, N, at least one in N-dimethyl amide, benzene and toluene.
9. the application of multipolymer claimed in claim 1 in organic solar batteries, organic electroluminescence device, organic field effect tube.
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|---|---|---|---|
| CN201210305596.7A CN103626969A (en) | 2012-08-24 | 2012-08-24 | Copolymer containing perylenetetracarboxylic diimide-s-indacenobithiophene, preparation method thereof and applications thereof |
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|---|---|---|---|
| CN201210305596.7A CN103626969A (en) | 2012-08-24 | 2012-08-24 | Copolymer containing perylenetetracarboxylic diimide-s-indacenobithiophene, preparation method thereof and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461923A (en) * | 2021-07-09 | 2021-10-01 | 万华化学集团股份有限公司 | Organic semiconductor initiator and application thereof in polylactic acid synthesis |
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2012
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461923A (en) * | 2021-07-09 | 2021-10-01 | 万华化学集团股份有限公司 | Organic semiconductor initiator and application thereof in polylactic acid synthesis |
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