CN102010500A - Novel N-ester substituted bisthiophene bispyridine conjugated polymer - Google Patents

Novel N-ester substituted bisthiophene bispyridine conjugated polymer Download PDF

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CN102010500A
CN102010500A CN2010105394514A CN201010539451A CN102010500A CN 102010500 A CN102010500 A CN 102010500A CN 2010105394514 A CN2010105394514 A CN 2010105394514A CN 201010539451 A CN201010539451 A CN 201010539451A CN 102010500 A CN102010500 A CN 102010500A
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pyrroles
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bithiophene
solar cell
ester group
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彭波
韦玮
高潮
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WUXI FEIDIYA PHOTOELECTRIC TECHNOLOGY Co Ltd
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Abstract

The invention discloses novel N-ester substituted bisthiophene bispyridine conjugated polymer, which belongs to the field of polymer solar cell materials. The conjugated polymer has a structural formula which is shown as a formula I, wherein R is straight-chain paraffin and branched paraffin of C6 to C12. By using the polymer as an electron donor material of a polymer solar cell, the highest occupied molecular orbital (HOMO) energy of the donor material can be effectively reduced, a photovoltaic device with high open-circuit voltage can be obtained, and the photoelectric conversion efficiency of the polymer solar cell can be improved.

Description

A kind of novel N-ester group replaces bithiophene and pyrroles's conjugated polymers
Technical field
The present invention relates to a kind of conjugated polymers that is used for the polymer solar battery electron donor material, belong to polymer solar battery material field.
Background technology
Polymer solar battery have cost low, in light weight, can curl, portable advantage, be the solar cell that has future most.The electrochemistry energy level matching of conjugated polymer material of electron donor material is poor, hole mobility is lower and absorption spectrum is narrower but the subject matter of restriction polymer solar battery development is to serve as.In order to address these problems, to adopt to have and the D-A-D conjugated polymers of aromatic ring structure can obtain the absorption spectrum widened and higher hole mobility, and pass through the meticulous modification and the adjusting of substituent structure, the electrochemical properties that can obtain to optimize.
For the conjugated polymer material that serves as electron donor(ED), difference between highest occupied molecular orbital energy level HOMO and the lowest unoccupied molecular orbital LUMO is the energy gap of polymkeric substance, this value is approximately little good more, and polymer materials could absorb sunlight as much as possible like this, increases short-circuit current; The HOMO energy should be low as far as possible in addition, can improve the open circuit voltage of polymer solar battery when being used with the electron acceptor material fullerene derivate like this.
The N-alkyl replaces bithiophene and pyrroles's conjugated polymers, is a kind of donor material with superperformance, is applied in polymer solar battery.As Kazuhito Hashimoto(Macromolecules 2008,41,8302-8305) wait bithiophene and pyrroles and 4 that the two iso-octyl of N-are replaced, 7-two (thiophene-2-yl)--2,1, the 3-diazosulfide carries out copolymerization, the D-A-D type multipolymer (PDTPDTBT that obtains, see the formula IV) highest occupied molecular orbital energy level (HOMO) be-5.00eV, lowest unoccupied molecular orbital energy level (LUMO) is-3.43eV, with fullerene derivate PC 61The open circuit voltage of the body heterojunction photovoltaic device that BM makes only is 0.52V, and efficient is 2.18%.If can continue to reduce the HOMO energy that N-replaces bithiophene and co-pyrrole copolymer, then the open circuit voltage of photovoltaic device can be improved, so the efficient of device still can continue to promote;
Figure 339334DEST_PATH_IMAGE001
Ⅳ。
Summary of the invention
The objective of the invention is to, at the problems referred to above, the present invention proposes to prepare the N-ester group and replaces bithiophene and pyrroles's conjugated polymers, regulates by substituent modification on the polymkeric substance nitrogen-atoms, further reduces the HOMO energy of conjugated polymers.
Technical scheme of the present invention is:
The N-ester group that is used for the polymer solar battery electron donor material replaces bithiophene and pyrroles's conjugated polymers, has suc as formula the structure shown in the I, and wherein R is straight chain and the branched-chain alkyl of C6 ~ C12;
Figure 375686DEST_PATH_IMAGE002
I。
As preferred construction, when R was n-hexyl, polymkeric substance had suc as formula the structure shown in the II;
Figure 551452DEST_PATH_IMAGE003
Ⅱ。
As preferred construction, when R was iso-octyl, polymkeric substance had suc as formula the structure shown in the III;
Figure 601317DEST_PATH_IMAGE004
Ⅲ。
The present invention is incorporated into N-with ester group and replaces on bithiophene and the pyrroles, and with novel short of electricity unit 1,3-two bromo-5-octyl group thiophene [3,4-c] and pyrroles-4, the 6-diketone carries out copolymerization, obtain the N-ester group and replace bithiophene and pyrroles D-A-D type conjugated polymers, compare with the duplex Thienopyrroles conjugated polymers that alkyl replaces, HOMO can further obtain reduction.Meanwhile,, can strengthen the rich electrical characteristic of duplex Thienopyrroles, more help the transmission of electric charge in D-A-D type conjugated polymers, reduce the energy gap of polymkeric substance because ester group has certain electrical characteristic of giving.
N-ester group disclosed by the invention replaces bithiophene and pyrroles's conjugated polymers, adopts suc as formula the reaction equation shown in the V synthetic.Wherein 1,3-two bromo-5-octyl group thiophene [3,4-c] and pyrroles-4, the method for synthesized reference J. Am. Chem Soc. 2010,132,5330 – 5331 of 6-diketone is synthetic, and its building-up reactions equation is seen the formula VI:
Figure 404055DEST_PATH_IMAGE005
Ⅴ。
Figure 527868DEST_PATH_IMAGE006
Ⅵ。
Specifically, preparation method of the present invention, key step is:
(1) with K 2CO 3, dimethyl-ethylenediamine, CuI place there-necked flask, adds toluene, stirs the alkyl substituted amide compound that adds behind the 30min under nitrogen protection, adds 3,3 '-two bromo-2 then, 2 '-bithiophene reacts 24h under the backflow situation.Behind the cool to room temperature, pour termination reaction in the water into, use hexane extraction, merge organic phase, dry back is removed and is desolvated, and is moving phase with hexane, and purification by silica gel column chromatography obtains white crystal shape compound N-alkyl formate base bithiophene and pyrroles 1.
(2) compound 1 and tetrahydrofuran (THF) are placed flask under nitrogen protection.N-Butyl Lithium at room temperature dropwise adds.Trimethyltin chloride subsequently (1M hexane solution) once adds.Being reflected at room temperature carried out 2 hours.Reactant is poured in the cold water, used extracted with diethyl ether, organic phase washes with water after merging, and is dry also except that after desolvating, and with ethyl alcohol recrystallization twice, obtains the two tin trimethyls 2 of N-alkyl formate base bithiophene and pyrroles.
(3) polyreaction
To wait the compound 2,1 of amount of substance, 3-two bromo-5-octyl group thiophene [3,4-c] and pyrroles-4, the 6-diketone places flask, and nitrogen protection adds toluene down, adds catalyst P d (PPh behind the 30min 3) 4, back flow reaction 24 hours.Pour reactant in methyl alcohol sedimentation, filter and collect the back, use the methyl alcohol sedimentation after the trichloromethane partial concentration, filter and collect, obtain the reddish black polymer powder after the oven dry with methyl alcohol, hexane and the extraction of trichloromethane Soxhlet.
Utilizing electrochemical workstation that the electrochemical properties of polymkeric substance is tested, is standard with the ferrocene, and the hexafluoro-phosphamide is an ionogen, and electrolytic solution is acetonitrile.The three-electrode system of employing standard is tested, with platinum filament as counter electrode, platinum dish as working electrode, Ag/Ag +As reference electrode.
When polymkeric substance of the present invention is used to prepare polymer solar battery, can carry out according to following process: polymkeric substance and C 60And derivative or other the material that can be used as electron acceptor(EA) mix mutually, add dissolution with solvents, on the ITO conductive glass, prepare one deck homogeneous film by spin coating or alternate manner, mode by vacuum evaporation prepares metal electrode on polymkeric substance then, can obtain polymer solar battery.
Utilize the N-ester group of technology preparation disclosed by the invention to replace duplex Thienopyrroles conjugated polymers, have low HOMO energy, be used for the electron donor material of polymer solar battery, with C 60, PC 61BM, PC 71Fullerene derivate electron acceptor materials such as BM cooperate can promote open circuit voltage effectively, and then promotes the photoelectric transformation efficiency of polymer solar battery.
Description of drawings
Accompanying drawing is used to provide further understanding of the present invention, and constitutes the part of specification sheets, is used from explanation the present invention with embodiments of the invention one, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is polymkeric substance II of the present invention and PC 61The I-V curve of the photovoltaic device that BM makes;
Fig. 2 is polymkeric substance III of the present invention and PC 61The I-V curve of the photovoltaic device that BM makes.
Embodiment
The present invention is further elaborated below by example, and purpose is to understand better content of the present invention, and the cited case does not limit protection scope of the present invention.
Embodiment 1
(1) preparation polymkeric substance II
1. with the K of 30mmol 2CO 3, the dimethyl-ethylenediamine of 2mmol, the CuI of 0.5mmol place there-necked flask, adds toluene 20mL, stirs the alkyl substituted amide compound that adds 12mmol behind the 30min under nitrogen protection; add 3 then; 3 '-two bromo-2,2 '-bithiophene 10mmol reacts 24h under the backflow situation.Behind the cool to room temperature, pour termination reaction in the water into, use hexane extraction, merge organic phase, dry back is removed and is desolvated, and is moving phase with hexane, and purification by silica gel column chromatography obtains white crystal shape compound N-formic acid hexyl ester group bithiophene and pyrroles.Proton nmr spectra (500MHz, CDCl 3): 7.2(d, 2H), 6.9 (d, 2H), 4.2(t, 2H), 1.57(m, 2H), 1.2～1.3(m, 6H), 0.96(t, 3H).
2. N-formic acid hexyl ester group bithiophene and pyrroles and 100mL tetrahydrofuran (THF) are placed flask under nitrogen protection.N-Butyl Lithium (13.2mmol, 2.2M hexane solution) at room temperature dropwise adds.The trimethyltin chloride of 14mmol (1M hexane solution) once adds subsequently.Being reflected at room temperature carried out 2 hours.Reactant is poured in the cold water, used extracted with diethyl ether, organic phase washes with water after merging, and is dry also except that after desolvating, and with ethyl alcohol recrystallization twice, obtaining the two tin trimethyls of N-formic acid hexyl ester group bithiophene and pyrroles is a colourless acicular crystal.Proton nmr spectra (500MHz, CDCl 3): 7.2(d, 2H), 4.16(t, 2H), 1.57(m, 2H), 1.2～1.3(m, 6H), 1.9～1.0(m, 21H).
3. polyreaction
With 1 of the N-formic acid hexyl ester group bithiophene of 2mmol and the two tin trimethyls of pyrroles, 2mmol, 3-two bromo-5-octyl group thiophene [3,4-c] and pyrroles-4, the 6-diketone places flask, and nitrogen protection adds toluene 20mL down, adds 22mg catalyst P d (PPh behind the 30min 3) 4, back flow reaction 24 hours.Pour reactant in methyl alcohol sedimentation, filter and collect the back, use the methyl alcohol sedimentation after the trichloromethane partial concentration, filter and collect, obtain reddish black polymer powder II 0.71g after the oven dry, yield 63% with methyl alcohol, hexane and the extraction of trichloromethane Soxhlet.
The number-average molecular weight Mn that gel permeation chromatography GPC records is 47652, and distribution coefficient PDI is 2.08.
(2) electrochemical properties
Utilizing electrochemical workstation that the electrochemical properties of polymkeric substance II is tested, is standard with the ferrocene, and the hexafluoro-phosphamide is an ionogen, and electrolytic solution is acetonitrile.The three-electrode system of employing standard is tested, with platinum filament as counter electrode, platinum dish as working electrode, Ag/Ag +As reference electrode.The HOMO that records the polymkeric substance II can be-5.13eV.
(3) polymer solar cell device performance
At the ito glass surface spin coating PEDOT:PSS layer that cleans up, oven dry back spin coating polymerization II and PC 61The o-dichlorobenzene solution of BM (polymkeric substance and PC in every ml soln 61Each 15mg of BM), treat the LiF layer of dried final vacuum evaporation 0.5nm and the Al electrode of 150nm, device is under vacuum condition 150 then oThe C 30min that anneals.The area of device photoactive layers is 0.314cm 2, the solar cell device that makes is under the solar cell simulator AM1.5 of Newport Thermal Oriel condition, and the photoelectric transformation efficiency that records with Keithly 2611 sources table is 2.19%, open circuit voltage V OcBe 0.77eV, short-circuit current density j Sc=6.06mA/cm 2, packing factor FF=0.47.The I-V curve is seen accompanying drawing 1.
Embodiment 2
(1) preparation polymkeric substance III
1. with the K of 30mmol 2CO 3, the dimethyl-ethylenediamine of 2mmol, the CuI of 0.5mmol place there-necked flask, adds toluene 20mL, stirs the alkyl substituted amide compound that adds 12mmol behind the 30min under nitrogen protection; add 3 then; 3 '-two bromo-2,2 '-bithiophene 10mmol reacts 24h under the backflow situation.Behind the cool to room temperature, pour termination reaction in the water into, use hexane extraction, merge organic phase, dry back is removed and is desolvated, and is moving phase with hexane, and purification by silica gel column chromatography obtains white crystal shape compound N-formic acid different monooctyl ester base bithiophene and pyrroles.Proton nmr spectra (500MHz, CDCl 3): 7.2(d, 2H), 6.9 (d, 2H), 3.9 ~ 4.2(m, 2H), 2.07(m, 1H), 1.2～1.3(m, 8H), 0.9 ~ 1.0(t, 6H).
2. compound N-formic acid different monooctyl ester base bithiophene and pyrroles and 100mL tetrahydrofuran (THF) are placed flask under nitrogen protection.N-Butyl Lithium (13.2mmol, 2.2M hexane solution) at room temperature dropwise adds.The trimethyltin chloride of 14mmol (1M hexane solution) once adds subsequently.Being reflected at room temperature carried out 2 hours.Reactant is poured in the cold water, used extracted with diethyl ether, organic phase washes with water after merging, and is dry also except that after desolvating, and with ethyl alcohol recrystallization twice, obtaining the two tin trimethyls of compound N-formic acid different monooctyl ester base bithiophene and pyrroles is a colourless acicular crystal.Proton nmr spectra (500MHz, CDCl 3): 7.0(d, 2H) 3.9 ~ 4.2(m, 2H), 2.0(m, 1H), 1.2～1.3(m, 8H), 0.9 ~ 1.0(m, 24H).
3. polyreaction
With the two tin trimethyls of 2mmolN-formic acid different monooctyl ester base bithiophene and pyrroles, 2mmol 1,3-two bromo-5-octyl group thiophene [3,4-c] and pyrroles-4, the 6-diketone places flask, and nitrogen protection adds toluene 20mL down, adds 22mg catalyst P d (PPh behind the 30min 3) 4, back flow reaction 24 hours.Pour reactant in methyl alcohol sedimentation, filter and collect the back, use the methyl alcohol sedimentation after the trichloromethane partial concentration, filter and collect, obtain reddish black polymer powder III 0.67g after the oven dry, yield 56% with methyl alcohol, hexane and the extraction of trichloromethane Soxhlet.
The number-average molecular weight Mn that GPC records is 38759, distribution coefficient PDI=1.94.
(2) chemical property
Utilizing electrochemical workstation that the electrochemical properties of polymkeric substance III is tested, is standard with the ferrocene, and the hexafluoro-phosphamide is an ionogen, and electrolytic solution is acetonitrile.The three-electrode system of employing standard is tested, with platinum filament as counter electrode, platinum dish as working electrode, Ag/Ag +As reference electrode.The HOMO that records the polymkeric substance III can be-5.18eV.
(3) polymer solar cell device performance
At the ito glass surface spin coating PEDOT:PSS layer that cleans up, oven dry back spin coating polymerization III and PC 61The o-dichlorobenzene solution of BM (polymkeric substance and PC in every ml soln 61Each 15mg of BM), treat the LiF layer of dried final vacuum evaporation 0.5nm and the Al electrode of 150nm, device is under vacuum condition 150 then oThe C 30min that anneals.The area of device photoactive layers is 0.314cm 2, the solar cell device that makes is under the solar cell simulator AM1.5 of Newport Thermal Oriel condition, and the photoelectric transformation efficiency that records with Keithly 2611 sources table is 2.34%, open circuit voltage V OcBe 0.75V, short-circuit current density j Sc=6.56mA/cm 2, packing factor FF=0.47.The I-V curve is seen accompanying drawing 2.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (4)

1. a novel N-ester group replaces bithiophene and pyrroles's conjugated polymers, it is characterized in that having suc as formula the structure shown in the I, and wherein R is straight chain and the branched-chain alkyl of C6 ~ C14;
Figure 2010105394514100001DEST_PATH_IMAGE001
I。
2. N-ester group according to claim 1 replaces bithiophene and pyrroles's conjugated polymers, it is characterized in that R is a n-hexyl.
3. N-ester group according to claim 1 replaces bithiophene and pyrroles's conjugated polymers, it is characterized in that R is an iso-octyl.
4. the described N-ester group of claim 1～3 replaces bithiophene and the application of pyrroles's conjugated polymers in the preparation of polymer solar battery electron donor material.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013028750A (en) * 2011-07-29 2013-02-07 Sumitomo Chemical Co Ltd Polymeric compound, and organic transistor using the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101407574A (en) * 2008-12-01 2009-04-15 中国科学院长春应用化学研究所 Donor-receptor type conjugated polymer containing dithiophen b pyrrole, preparation method and application thereof
CN101671428A (en) * 2008-09-09 2010-03-17 中国科学院化学研究所 Conjugated polymer based on condensed ring thiophene and diazosulfide as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101671428A (en) * 2008-09-09 2010-03-17 中国科学院化学研究所 Conjugated polymer based on condensed ring thiophene and diazosulfide as well as preparation method and application thereof
CN101407574A (en) * 2008-12-01 2009-04-15 中国科学院长春应用化学研究所 Donor-receptor type conjugated polymer containing dithiophen b pyrrole, preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013028750A (en) * 2011-07-29 2013-02-07 Sumitomo Chemical Co Ltd Polymeric compound, and organic transistor using the same

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