CN110218297A - A kind of two dimension conjugation benzene thiophene and furans pyrazine copolymer, preparation method and application - Google Patents

A kind of two dimension conjugation benzene thiophene and furans pyrazine copolymer, preparation method and application Download PDF

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CN110218297A
CN110218297A CN201910499025.3A CN201910499025A CN110218297A CN 110218297 A CN110218297 A CN 110218297A CN 201910499025 A CN201910499025 A CN 201910499025A CN 110218297 A CN110218297 A CN 110218297A
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furans
bis
pyrazine
benzene thiophene
copolymer
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刘波
陈远道
王晓波
王钢
刘骏
何敏
胡霞
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Hunan University of Arts and Science
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Hunan University of Arts and Science
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Abstract

The present invention disclose it is a kind of two dimension conjugation benzene thiophene and furans pyrazine copolymer, preparation method and application, structural formula it is as follows:Wherein R is alkyl, and copolymer of the invention is electron donor material, is applied to polymer solar battery, absorbs with wide visible region, lower HOMO energy level, relatively narrow band gap and higher photoelectric conversion efficiency.

Description

It is a kind of two dimension conjugation benzene thiophene and furans pyrazine copolymer, preparation method and Using
Technical field
The present invention relates to Polymer photovoltaic materials technical fields, and in particular to a kind of two dimension conjugation benzene thiophene and furans Pyrazine copolymer, preparation method and application.
Background technique
As getting worse for global warming phenomenon faces exhaustion, the world with fossil energy (coal, oil and natural gas etc.) Is taken to the discharge amount of carbon dioxide by stringent control for various countries.Therefore, solar energy is more next as a kind of renewable and clean energy resource More obtain the attention of global scientific circles and industrial circle.The one kind of polymer solar cells as novel solar cell, recent two decades It is achieved quickly to be prepared into the advantages such as large area flexible device in such a way that its distinctive device quality is light and printing can be used Development, become one of the hot spot of Present Global energy field research.
The progress of polymer solar battery material, Li Yongxi etc., Journal of Functional Polymers, are retouched in December, 2014 The structural formula for having stated the various typical materials of D-A system, it mainly includes following for also describing the design of donor polymer material Several aspects: (1) higher open-circuit voltage and short circuit current are obtained by regulate and control energy level and the band gap of polymer material；(2) The flatness for improving polymer material increases its charge mobility, but in this process, it is to be ensured that the dissolubility of material and Stability.These factors are interrelated, ideally, it should optimize simultaneously to these factors, but actually this is very Difficult.Therefore, finding an equalization point makes battery obtain maximum incident photon-to-electron conversion efficiency, be materialized scholar design polymer to The key of body material.During designing organic solar batteries polymer material, following several principles: (1) gathering Relatively narrow band gap should be had by closing object；(2) higher molar extinction coefficient；(3) good flatness；(4) high charge moves Shifting rate；(5) preferable photostability.Meanwhile higher molecular weight, higher charge mobility, optimization pattern, filling because Son etc. can influence the performance of material.Usually, the structure of conjugated polymer is divided into following 3 parts: altogether Conjugated polymer main chain, side chain and substituent group.Also disclose the common compounds of the polymer battery material of different band gaps.
Current one of the development sixty-four dollar question for hindering binode battery is the absence of the smart polymeric of high-performance, low band gaps Material.In order to solve this problem, a kind of method is the quinoid structure for increasing main polymer chain, to obtain narrow band gap polymer. Quinoid polymer is usually to be connected in parallel on the same structural unit to be formed by 2 or 2 or more distinct fragrance compounds 's.It will use the biggish armaticity structure of resonance energy, to make another armaticity structure using quinoid structure.Due to phenyl ring Resonance energy (1.56eV) is greater than the resonance energy (1.26eV) of thiophene, and thiophene unit will use quinoid structure.Because quinoid structure Resonance energy is low compared with armaticity structure, so the band gap of polymer can be effectively reduced using quinoid structure.Polyphenyl bithiophene Band gap there was only 1.1eV, the band gap of polythiophene and piperazine is 0.95eV, and the band gap of polythieno-thiophene is only There is 0.8-0.9eV.Although this quasi polymer band gap is minimum, this method is preparing narrow band gap polymer solar electricity There is its limitation during the material of pond, because the HOMO energy level of this quasi polymer is usually higher, based on their sun The open-circuit voltage very little of energy battery device, significantly limits the raising of incident photon-to-electron conversion efficiency.
Chinese Patent Application No. is that the patent of 201510807862.X discloses photovoltaic film material, is indole derivatives With the double tin copolymers of benzene thiophene, structural formula is as follows:
The photoelectric conversion efficiency of this compound is not high enough, limits the application of substance of this kind.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of two dimension conjugation benzene thiophene and furans pyrazine copolymers, system Preparation Method and application absorb, lower HOMO energy level with wide visible region, relatively narrow band gap and higher Photoelectric conversion efficiency.
Contents of the present invention structural formula is as follows:
Wherein R is alkyl.
Preferably, the two dimension conjugation benzene thiophene and the number-average molecular weight of furans pyrazine copolymer are 13100- 23000, weight average molecular weight 29600-60400, PDI (polymer dispersity index) are 2.3-2.6.
Preferably, the R is the linear chain or branched chain alkane of 8~20 carbon atoms.
Preferably, the R is substituent group:
A kind of preparation method of two dimension conjugation benzene thiophene and furans pyrazine copolymer, comprising the following steps:
1) Isosorbide-5-Nitrae-diacetyl piperazine -2,5- diketone, 5-bromo-2-furaldehyde and organic solvent mixing, are added triethylamine, Reaction, cooling, precipitating filters, and washing obtains bis- ((5- bromine furans -2-) methylene) piperazine -2, the 5- diketone of 3,6-；
2) 3,6- bis- ((5- bromine furans -2-) methylene) piperazine-2,5-dione, potassium carbonate and brominated alkanes are in organic solvent Mixing, heating is cooling after reaction, and mixture is extracted, dry, and separation obtains bis- ((the 5- bromines of 2,5- dialkoxy -3,6- Furans -2-) methylene) pyrazine；
3) by 2,6- bis- (tin trimethyl) -4,8- two (2- iso-octyl-thienyl)-benzo (1,2-b；4,5-b ') Dithiophene It is added in dry toluene with bis- ((the 5- bromine furans -2-) methylene) pyrazines of 2,5- dialkoxy -3,6-, adds four (triphens Base phosphine) palladium, cooling after reaction, precipitating filters, and extracts, and obtains two dimension conjugation benzene thiophene and furans pyrazine copolymer.
Preferably, the molar ratio of Isosorbide-5-Nitrae-diacetyl piperazine -2,5- diketone and 5-bromo-2-furaldehyde is 1 in step 1): 2~3.
Preferably, brominated alkanes described in step 2) be bromo-iso-octane, bromooctane or bromo 2- octyl-dodecane, The molar ratio of bis- ((the 5- bromine furans -2-) methylene) piperazine-2,5-diones of 3,6- and brominated alkanes is 1:3~4.
Preferably, reaction temperature is 100~120 DEG C in step 3).
The present invention also provides a kind of two dimension conjugation benzene thiophene and furans pyrazine copolymer answering in solar cells With the two dimension conjugation benzene thiophene and furans pyrazine copolymer are used as in solar battery as electron donor material.
In the present invention, when R isWhen, the subject polymer of synthesis is (the 2- iso-octyl-thiophene of 4,8- bis- Pheno base)-benzo (1,2-b；4,5-b ') bis- (furans -2- methylene) pyrazines (P1) of two different octyloxy -3,6- of-Dithiophene -2,5-.
When R isWhen, the subject polymer of synthesis is 4,8- bis- (2- iso-octyl-thienyl)- Benzo (1,2-b；4,5-b ') bis- (furans -2- methylene) pyrazines (P2) of two octyloxy -3,6- of-Dithiophene -2,5-.
When R isWhen, the subject polymer of synthesis is (the 2- iso-octyl-of 4,8- bis- Thienyl)-benzo (1,2-b；4,5-b ') bis- (furans -2- methylenes of-Dithiophene -2,5- two (2- octyldodecyl oxygroup) -3,6- Base) pyrazine (P3).
Copolymer of the invention has good machinability, and attempts to prove that there is preferable photoelectricity to turn by preliminary Characteristic is changed, the working media as polymer solar battery has broad application prospects.
Specifically, preparation method of the invention, comprising the following steps:
1) under argon gas protection, Isosorbide-5-Nitrae-diacetyl piperazine -2,5- diketone and 5-bromo-2-furaldehyde are blended in DMF, Triethylamine is added at 120 DEG C, reacts 12 hours, is cooled to room temperature, precipitating, filters, washing obtains bis- ((the 5- bromothiophenes-of 3,6- 2-) methylene) piperazine-2,5-dione；
2) under argon gas protection, 3,6- bis- ((5- bromine furans -2-) methylene) piperazine -2,5- diketone, potassium carbonate and bromoalkanes Hydrocarbon, which is warming up at 100 DEG C in DMF, to react 2 hours, is cooled to room temperature, pours the mixture into water, extracts, dry, is spin-dried for molten Agent crosses silicagel column, obtains bis- ((the 5- bromine furans -2-) methylene) pyrazines of 2,5- dialkoxy -3,6-；
3) under nitrogen protection, by 2,6- bis- (tin trimethyl) -4,8- bis- (2- iso-octyl-thienyl)-benzo (1,2-b；4, 5-b ') Dithiophene and bis- ((the 5- bromine furans -2-) methylene) pyrazines of 2,5- dialkoxy -3,6- are added in dry toluene, then Pd (PPh is added3)4(tetrakis triphenylphosphine palladium) is reacted 24 hours at 115 DEG C, is cooled to room temperature, precipitating, filter, Soxhlet extraction, Obtain present copolymer.
Wherein, shown in the structural formula such as following formula (1) of bis- ((5- bromine furans -2-) methylene) piperazine -2, the 5- diketone of 3,6-:
Shown in the structural formula such as following formula (2) of bis- ((the 5- bromine furans -2-) methylene) pyrazines of 2,5- dialkoxy -3,6-:
2,6- bis- (tin trimethyl) -4,8- two (2- iso-octyl-thienyl)-benzo (1,2-b；4,5-b ') Dithiophene knot Structure formula is shown below:
The synthetic route of copolymer of the invention is as follows:
i)NEt3,DMF,120℃,12h；ii)RBr,K2CO3,DMF,100℃,2h；iii)Pd(PPh3)4,toluene, 115℃。
The preparation method of two dimension conjugation benzene thiophene and furans pyrazine copolymer of the invention is coupled using Stille Method, FAQM electron acceptor unit and BDTT electron donor unit are directly coupled.
The present invention has synthesized a kind of FAQM electron acceptor unit containing different alkyloxy side chains, passes through Stille coupling FAQM unit is connected by carbon-to-carbon singly-bound with another electron donor unit B DTT by method, obtains two dimension conjugation benzo two Thiophene and furans pyrazine copolymer.They have good molten in common organic solvent (such as toluene, chlorobenzene, tetrahydrofuran) Xie Xing can use the thin polymer film of the method preparation high quality of solution spin coating.Meanwhile these Polymer photovoltaic materials have width Visible light-near infrared region absorb, suitable HOMO and lumo energy and relatively narrow band gap.It is electricity with this quasi polymer Sub- donor, PC61BM or small organic molecule are that electron acceptor is prepared for polymer solar battery, and highest energy transfer efficiency can Reach 5.5%, there is good photoelectric conversion efficiency.
The present invention is electron donor material with above-mentioned two dimension conjugation benzene thiophene and furans pyrazine copolymer, is applied to poly- Object solar battery is closed, preparation method is as follows:
By two dimension conjugation benzene thiophene of the invention and furans pyrazine analog copolymer electron donor material and electron acceptor (PC61BM or small organic molecule) substance blending, chlorobenzene is added, dissolves mixture sufficiently, is spin-coated on electro-conductive glass ITO and prepares Conductive film out, then the evaporation metal aluminium electrode on film.
Two dimension conjugation benzene thiophene provided by the invention and furans pyrazine copolymer are with wide absorption spectrum and properly Electrochemistry energy level, and characterize with nuclear magnetic resoance spectrum, mass spectrum and the method for elemental analysis the molecular structure of each step synthetic product. With uv-visible absorption spectra have studied two dimension conjugation benzene thiophene and furans pyrazine analog copolymer photovoltaic material it is optical Energy.The chemical property of two dimension conjugation benzene thiophene and furans pyrazine copolymer is had studied, and with cyclic voltammetry with its work It has been made into solar cell device for electron donor, has obtained good photoelectric conversion efficiency.
Compared with prior art, the invention has the following advantages:
(1) route that the present invention synthesizes is simple, at low cost, and synthetic method has universality, can preferably promote and answer Use the synthesis of other AQM class photovoltaic materials.
(2) FAQM quasi polymer photovoltaic material of the invention has wide uv-visible absorption spectra, can ensure absorption foot Enough solar photons obtain high photoelectric current.
(3) FAQM quasi polymer photovoltaic material of the invention has lower HOMO energy level, high to the stability of oxygen, favorably In the solar cell device that processability is more stable.
(4) present invention is electron donor material with two dimension conjugation benzene thiophene and furans pyrazine copolymer photovoltaic material, Higher energy conversion efficiency (PCE=5.5%) is obtained applied to polymer solar battery, before there is good application Scape.
Detailed description of the invention
Fig. 1 is the absorption spectrum of present invention two dimension conjugation benzene thiophene and furans pyrazine copolymer.
Fig. 2 is the cyclic voltammetry curve of present invention two dimension conjugation benzene thiophene and furans pyrazine copolymer.
Fig. 3 is the photoelectric conversion efficiency figure of present invention two dimension conjugation benzene thiophene and furans pyrazine copolymer.
Specific embodiment
Embodiment 1
4,8- bis- (2- iso-octyl-thienyl)-benzo (1,2-b；4,5-b ') two different octyloxy -3,6- of-Dithiophene -2,5- The preparation of bis- (furans -2- methylene) pyrazines (P1).
Specific step is as follows:
1. the synthesis of compound 1
By Isosorbide-5-Nitrae-diacetyl piperazine -2,5- diketone (1.19g, 6mmol) and bromo- 2 furtural of 5- (2.63g, It 15mmol) is placed in the single necked round bottom flask of 50ml, then addition 28ml DMF, under nitrogen protection, heating stirring is warming up to 120 DEG C, triethylamine 3.32ml is added by syringe, after, reaction system immediately becomes red from colourless, and the reaction was continued 12 Hour, it after the reaction was completed, is cooled to room temperature, generates yellow mercury oxide, precipitating is collected by filtration, with acetone washing, collect product, obtain (yield: 84%) 2.16g does not need to be further purified directly progress next step reaction to target product.
Nuclear magnetic resoance spectrum, the mass spectrum of compound 1 are as follows:
1H NMR (400MHz, d-DMSO, ppm): δ=9.83 (s, 2H), 7.23 (d, 2H), 6.74 (s, 2H), 6.45 (d, 2H).
GC-MS:m/z=428.
2. the synthesis of compound 2
Bis- ((5- bromine furans -2-) methylene) piperazine -2, the 5- diketone of 3, the 6- that previous step is reacted (1.4g, 3.26mmol), potassium carbonate (2.25g, 16.3mmol) and bromo-iso-octane (2.51g, 13mmol) are mixed into 30ml DMF, nitrogen Under gas shielded, 120 DEG C are warming up to, is stirred to react 2h, after completion of the reaction, is cooled to room temperature, solid is filtered out, collects filtrate, is used Extra DMF is removed in methylene chloride extraction, washing, and crude product is purified using the method that column chromatographs, petroleum ether: methylene chloride=5: 1 is leacheate, obtains orange solids 2, (1.1g is produced bis- ((the 5- bromine furans -2-) methylene) pyrazines of the different octyloxy -3,6- of 5- bis- Rate: 53%).
Nuclear magnetic resoance spectrum, the mass spectrum of compound 2 are as follows:
1H NMR(400MHz,CDCl3, ppm): δ=7.20 (d, 2H), 6.76 (s, 2H), 6.46 (d, 2H), 4.27 (t, 4H),1.80(m,2H),1.53-1.36(m,16H),0.98-0.89(m,12H)。
GC-MS:m/z=652.
3. the synthesis of polymer P 1
Under nitrogen protection, by the compound 2 and 2 of equimolar amounts, 6- bis- (tin trimethyl) -4,8- bis- (2- iso-octyl-thiophene Base)-benzo (1,2-b；4,5-b ') Dithiophene (0.1mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added to 10ml without In water-toluene, Pd (PPh is added3)4(10mg) is cooled to room temperature after being stirred to react 48 hours at 110 DEG C, pours into 100ml first Precipitating in alcohol, filtering, crude product are once extracted by methanol, n-hexane and chloroform, and obtaining blue solid P1, (83mg is produced Rate 80%)；Wherein R group is as follows in polymer P 1:
The gel osmoticing chromatogram analysis of polymer P 1 is as follows:
Mn=13100, Mw=29600, PDI=2.3.
Embodiment 2 4,8- bis- (2- iso-octyl-thienyl)-benzo (1,2-b；4,5-b ') two pungent oxygen of-two furans -2,5- The preparation of bis- (furans -2- methylene) pyrazines (P2) of base -3,6-
The synthetic method of compound 2 is identical as the synthetic method of compound 2 in embodiment 1, and brominated alkanes are using bromo just Octane, the specific steps are as follows:
1. the synthesis of compound 1
By Isosorbide-5-Nitrae-diacetyl piperazine -2,5- diketone (1.19g, 6mmol) and bromo- 2 furtural of 5- (2.63g, It 15mmol) is placed in the single necked round bottom flask of 50ml, then addition 28ml DMF, under nitrogen protection, heating stirring is warming up to 120 DEG C, triethylamine 3.32ml is added by syringe, after, reaction system immediately becomes red from colourless, and the reaction was continued 12 Hour, it after the reaction was completed, is cooled to room temperature, generates yellow mercury oxide, precipitating is collected by filtration, with acetone washing, collect product, obtain (yield: 84%) 2.16g does not need to be further purified directly progress next step reaction to target product.
Nuclear magnetic resoance spectrum, the mass spectrum of compound 1 are as follows:
1H NMR (400MHz, d-DMSO, ppm): δ=9.83 (s, 2H), 7.23 (d, 2H), 6.74 (s, 2H), 6.45 (d, 2H).
GC-MS:m/z=428.
2. the synthesis of compound 2
Bis- ((5- bromine furans -2-) methylene) piperazine -2, the 5- diketone of 3, the 6- that previous step is reacted (1.4g, 3.26mmol), potassium carbonate (2.25g, 16.3mmol) and bromooctane (2.51g, 13mmol) are mixed into 30ml DMF, nitrogen Under protection, 120 DEG C are warming up to, is stirred to react 2 hours, after completion of the reaction, is cooled to room temperature, filters out solid, collects filtrate, is used Extra DMF is removed in methylene chloride extraction, washing, and crude product is purified using the method that column chromatographs, petroleum ether: methylene chloride=5: 1 is leacheate, obtains orange solids 2, (0.79g is produced bis- ((the 5- bromine furans -2-) methylene) pyrazines of the different octyloxy -3,6- of 5- bis- Rate: 37%).
Nuclear magnetic resoance spectrum, the mass spectrum of compound 2 are as follows:
1H NMR(400MHz,CDCl3, ppm): δ=7.19 (d, 2H), 6.77 (s, 2H), 6.48 (d, 2H), 4.26 (t, 4H),1.55-1.38(m,26H),0.98-0.89(m,6H).
GC-MS:m/z=652.
3. the synthesis of polymer P 2
Under nitrogen protection, by the compound 2 and 2 of equimolar amounts, 6- bis- (tin trimethyl) -4,8- bis- (2- iso-octyl-thiophene Base)-benzo (1,2-b；4,5-b ') Dithiophene (0.1mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added to 10mL without In water-toluene, Pd (PPh is added3)4(10mg) is cooled to room temperature after being stirred to react 48 hours at 110 DEG C, pours into 100ml first Precipitating in alcohol, filtering, crude product are once extracted by methanol, n-hexane and chloroform, and obtaining blue solid P2, (86mg is produced Rate 83%)；Wherein R group is as follows in polymer P 2:
The gel osmoticing chromatogram analysis of polymer P 2 is as follows:
Mn=15,100, Mw=34,900, PDI=2.3.
Embodiment 3 4,8- bis- (2- iso-octyl-thienyl)-benzo (1,2-b；4,5-b ') (2- is pungent by-two furans -2,5- two Base dodecyloxy) bis- (furans -2- methylene) pyrazines (P3) of -3,6- preparation
The synthetic method of compound 2 is identical as the synthetic method of compound 2 in embodiment 1, and brominated alkanes use bromo 2- Octyl-dodecane, the specific steps are as follows:
1. the synthesis of compound 1
By Isosorbide-5-Nitrae-diacetyl piperazine -2,5- diketone (1.19g, 6mmol) and bromo- 2 furtural of 5- (2.63g, It 15mmol) is placed in the single necked round bottom flask of 50ml, then addition 28ml DMF, under nitrogen protection, heating stirring is warming up to 120 DEG C, triethylamine 3.32ml is added by syringe, after, reaction system immediately becomes red from colourless, and the reaction was continued 12 Hour, it after the reaction was completed, is cooled to room temperature, generates yellow mercury oxide, precipitating is collected by filtration, with acetone washing, collect product, obtain (yield: 84%) 2.16g does not need to be further purified directly progress next step reaction to target product.
Nuclear magnetic resoance spectrum, the mass spectrum of compound 1 are as follows:
1H NMR (400MHz, d-DMSO, ppm): δ=9.83 (s, 2H), 7.23 (d, 2H), 6.74 (s, 2H), 6.45 (d, 2H).
GC-MS:m/z=428.
2. the synthesis of compound 2
Bis- ((5- bromine furans -2-) methylene) piperazine -2, the 5- diketone of 3, the 6- that previous step is reacted (1.4g, 3.26mmol), potassium carbonate (2.25g, 16.3mmol) and bromo 2- octyl-dodecane (4.69g, 13mmol) are mixed into 30ml In DMF, under nitrogen protection, 120 DEG C are warming up to, is stirred to react 2 hours, after completion of the reaction, is cooled to room temperature, filters out solid, Filtrate is collected, is extracted with dichloromethane, extra DMF is removed in washing, and crude product is purified using the method that column chromatographs, petroleum ether: Methylene chloride=5:1 is leacheate, obtains orange solids 2, the different octyloxy -3,6- of 5- bis- is bis- ((5- bromine furans -2-) methylene) Pyrazine (0.81g, yield: 25%).
Nuclear magnetic resoance spectrum, the mass spectrum of compound 2 are as follows:
1H NMR(400MHz,CDCl3, ppm): δ=7.25 (d, 2H), 6.79 (s, 2H), 6.49 (d, 2H), 4.28 (t, 4H),1.85(m,2H),1.57-1.34(m,64H),0.97-0.88(m,12H).
GC-MS:m/z=652.
3. the synthesis of polymer P 3
Under nitrogen protection, by the compound 2 and 2 of equimolar amounts, 6- bis- (tin trimethyl) -4,8- bis- (2- iso-octyl-thiophene Base)-benzo (1,2-b；4,5-b ') Dithiophene (0.1mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added to 10mL without In water-toluene, Pd (PPh is added3)4(10mg) is cooled to room temperature after being stirred to react 48 hours at 110 DEG C, pours into 100ml first Precipitating in alcohol, filtering, crude product are once extracted by methanol, n-hexane and chloroform, and obtaining blue solid P3, (128mg is produced Rate 93%)；Wherein R group is as follows in polymer P 3:
The gel osmoticing chromatogram analysis of polymer P 3 is as follows:
Mn=23000, Mw=60400, PDI=2.6.
The preparation of 4 polymer solar battery of embodiment
The present invention prepares solar-electricity using two dimension conjugation benzene thiophene and furans pyrazine analog copolymer as working media The method in pond is: by above-mentioned two dimension conjugation benzene thiophene and furans Pyrazine copolymer material and suitable PC61BM (fowler Alkene) or other material mixings that can be used as electron acceptor, suitable solvent dissolution is added, ITO is spin-coated on by conventional One layer of translucent film is prepared on (tin indium oxide) electro-conductive glass, then in photovoltaic active layers by way of vacuum evaporation On prepare metal electrode.
Specific steps are as follows: the polymer P 1 of 1.0mg and the PC of 2.0mg61BM mixing is added the dissolution of 0.15mL chlorobenzene, passes through Spin coating mode prepares the film of one layer of about 100nm thickness on the electro-conductive glass through PEDOT:PSS modified, then passes through vacuum The mode of vapor deposition prepares metal electrode with aluminium/lithium fluoride on photovoltaic active layers.Its polymer solar cell device performance table It is existing are as follows:
Short circuit current=11.4mA/cm2；Open-circuit voltage=0.79V；Fill factor=60%；Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=5.5%.
The preparation of 5 polymer solar battery of embodiment
The polymer P 2 of 1.0mg and the PC of 2.0mg61BM mixing is added the dissolution of 0.15mL chlorobenzene, is being passed through by spin coating mode The film that one layer of about 100nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium/lithium fluoride prepares metal electrode on photovoltaic active layers.Its polymer solar cell device performance are as follows:
Short circuit current=10.7；Open-circuit voltage=0.79；Fill factor=60%；Simulated solar irradiation (A.M.1.5, 100mW/cm2) under energy conversion efficiency=5.2%.
The preparation of 6 polymer solar battery of embodiment
The polymer P 3 of 1.0mg and the PC of 2.0mg61BM mixing is added the dissolution of 0.15mL chlorobenzene, is being passed through by spin coating mode The film that one layer of about 110nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium/lithium fluoride prepares metal electrode on photovoltaic active layers.Its polymer solar cell device performance are as follows:
Short circuit current=9.7；Open-circuit voltage=0.79；Fill factor=58%；Simulated solar irradiation (A.M.1.5,100mW/ cm2) under energy conversion efficiency=4.5%.
Embodiment 7
By taking polymer P 1 as an example, absorption spectroanalysis, chemical property analysis, photovoltaic performance analysis are carried out to it.
1. the spectrum analysis of polymer P 1
Polymer P 1 is in the absorption spectrum under chloroform soln and filminess as shown in Figure 1, prepared by the embodiment 7 Filminess under, polymer P 1 has an obvious absorption in 300-830nm range interior focusing, and optics with gap is 1.49eV, illustrate to gather Closing object P1 is narrow with gap photovoltaic material, and more sunlights can be absorbed, obtain high short circuit current.Relatively narrow energy gap is mainly returned Cause is introduced into A-D type polymer in BDTT electron donor unit, forms Intramolecular electron transfer state, so that band gap is reduced, Reach broader light absorption range.The FAQM quasi polymer photovoltaic material of this class two-dimensional conjugation has in the preparation of solar battery Wide application prospect.
2. the chemical property of polymer P 1
In electrochemistry, cyclic voltammetry is usually used to the electrochemistry energy level of measurement substance, and Fig. 2 is that polymer P 1 exists The Bu of 0.1mol/L4NBF4/CH3The cyclic voltammetry curve measured in CN solution can find out polymer P 1 from oxidation curved portion Initial oxidation potential be 0.77V, corresponding HOMO energy level be -5.07eV, from reduction the available polymer P 1 of curved portion Initial reduction current potential be -0.57V, corresponding lumo energy be -3.73eV, electrochemistry energy gap be 1.34eV, referring to table 1.It is low HOMO energy level show that polymer P 1 has good air stability, be very suitable to preparation the long life solar battery device Part.
The optics and electrochemical results of 1 polymer P 1 of table
3. the photovoltaic performance of polymer P 1 is analyzed
The photovoltaic performance of polymer P 1 is as shown in Figure 3, the results showed that polymer P 1 has good photovoltaic performance.Such as polymerization Object P1 and PC61When BM is blended, short circuit current=11.4mA/cm2；Open-circuit voltage=0.79V；Fill factor=60%；Simulation is too Sunlight (A.M.1.5,100mW/cm2) under energy conversion efficiency=5.5%.It is believed that the transfer efficiency of solar battery can Further to be promoted by the optimization of device conditions.
It is at low cost by embodiment 1-7 it is found that the route that synthesizes of the present invention is simple, and synthetic method has universality, it can be with Preferably promote the use of the synthesis of other AQM class materials；The FAQM quasi polymer photovoltaic material of two dimension conjugation of the invention Resonant energy transfer is generated with strong push-and-pull electronic action, is expected to obtain broader uv-visible absorption spectra；Of the invention The FAQM quasi polymer photovoltaic material of two dimension conjugation has lower HOMO energy level, high to the stability of oxygen, is conducive to preparative Solar cell device that can be more stable；The present invention is electron donor with two dimension conjugation FAQM organic micromolecule photovoltaic material Material obtains higher energy conversion efficiency (PCE=5.5%) applied to organic molecule solar cell, has good Application prospect.
In conclusion the present invention has synthesized a kind of FAQM organic electronic receptor unit containing different alkyloxy side chains, lead to The method for crossing Stille coupling, FAQM receptor unit is connected by carbon-to-carbon singly-bound with another electron donor unit B DTT, Obtain the FAQM quasi polymer photovoltaic material of two dimension conjugation.They common organic solvent (such as methylene chloride, chloroform, Tetrahydrofuran etc.) in have good dissolubility, can use solution methods preparation high quality film.Meanwhile these polymer lights Lying prostrate material has wide visible region absorption, suitable HOMO and lumo energy and relatively narrow band gap.With this Type of Collective Object electron donor, PC61BM or organic matter electron acceptor are that electron acceptor is prepared for polymer solar battery, and highest energy turns Changing efficiency can reach 5.5%, have good photoelectric conversion efficiency.
It should be understood by those ordinary skilled in the art that: the discussion of any of the above embodiment is exemplary only, not It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under thinking of the invention, above embodiments Or it can also be combined between the technical characteristic in different embodiments, and there are different aspects present invention as described above Many other variations, in order to it is concise they do not provided in details.Therefore, all within the spirits and principles of the present invention, Any omission, modification, equivalent replacement, improvement for being made etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of two dimension conjugation benzene thiophene and furans pyrazine copolymer, characterized in that structural formula is as follows:
Wherein R is alkyl.
2. two dimension conjugation benzene thiophene as described in claim 1 and furans pyrazine copolymer, characterized in that the two dimension is altogether Yoke benzene thiophene and the number-average molecular weight of furans pyrazine copolymer are 12000-24000, weight average molecular weight 28000- 62000, PDI 2.2-2.7.
3. two dimension conjugation benzene thiophene as described in claim 1 and furans pyrazine copolymer, characterized in that the R is 8~ The linear chain or branched chain alkane of 20 carbon atoms.
4. two dimension conjugation benzene thiophene as described in claim 1 and furans pyrazine copolymer, characterized in that the R is to take Dai Ji:
5. a kind of preparation side of two dimension conjugation benzene thiophene and furans pyrazine copolymer according to any one of claims 1-4 Method, which comprises the following steps:
1) Isosorbide-5-Nitrae-diacetyl piperazine -2,5- diketone, 5-bromo-2-furaldehyde and organic solvent mixing, are added triethylamine, instead It answers, cooling, precipitating filters, and washing obtains bis- ((5- bromine furans -2-) methylene) piperazine -2, the 5- diketone of 3,6-；
2) bis- ((5- bromine furans -2-) methylene) piperazine-2,5-dione, potassium carbonate and the brominated alkanes of 3,6- are mixed in organic solvent It closes, heating is cooling after reaction, and mixture is extracted, and dry, separation obtains bis- ((the 5- bromine furans of 2,5- dialkoxy -3,6- Mutter -2-) methylene) pyrazine；
3) by 2,6- bis- (tin trimethyl) -4,8- two (2- iso-octyl-thienyl)-benzo (1,2-b；4,5-b ') Dithiophene and 2, Bis- ((the 5- bromine furans -2-) methylene) pyrazines of 5- dialkoxy -3,6- are added in dry toluene, add four (triphenylphosphines) Palladium, cooling after reaction, precipitating filters, and extracts, and obtains two dimension conjugation benzene thiophene and furans pyrazine copolymer.
6. preparation method according to claim 5, which is characterized in that Isosorbide-5-Nitrae-diacetyl piperazine -2,5- bis- in step 1) The molar ratio of ketone and 5-bromo-2-furaldehyde is 1:2~3.
7. preparation method according to claim 5, which is characterized in that brominated alkanes described in step 2) are that bromo is different pungent Alkane, bromooctane or bromo 2- octyl-dodecane, 3,6- bis- ((5- bromine furans -2-) methylene) piperazine -2,5- diketone and bromo The molar ratio of alkane is 1:3~4.
8. preparation method according to claim 5, which is characterized in that reaction temperature is 100~120 DEG C in step 3).
9. a kind of two dimension conjugation benzene thiophene according to any one of claims 1-4 and furans pyrazine copolymer are in solar energy Application in battery.
10. application according to claim 9, which is characterized in that the two dimension conjugation benzene thiophene and furans pyrazine are total Polymers, which is used as in solar battery, is used as electron donor material.
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