CN102827358B - Conjugated polymer of 4,8-di(5-isooctyl thiophene)phenyl [1,2-b; 3,4-b]bithiophene and chloroquinoxaline - Google Patents

Conjugated polymer of 4,8-di(5-isooctyl thiophene)phenyl [1,2-b; 3,4-b]bithiophene and chloroquinoxaline Download PDF

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CN102827358B
CN102827358B CN201210316937.0A CN201210316937A CN102827358B CN 102827358 B CN102827358 B CN 102827358B CN 201210316937 A CN201210316937 A CN 201210316937A CN 102827358 B CN102827358 B CN 102827358B
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bithiophene
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thiophene
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CN102827358A (en
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高潮
武海梅
王维平
田地
丛志远
安忠维
弥育华
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Xian Modern Chemistry Research Institute
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Abstract

The invention belongs to the functional polymer material field, and concretely relates to a conjugated polymer of 4,8-di(5-isooctyl thiophene)phenyl [1,2-b; 4, 5-b]bithiophene and chloroquinoxaline, a structural general formula of the conjugated polymer is shown as I. The polymer is prepared by a Stille coupling reaction of dibromo chloroquinoxaline and 2,6-di(trimethyl)-4,8-di(5- isooctyl thiophene)phenyl [1,2-b; 4, 5-b]bithiophene, and is used for an electron donor material of a polymer heterojunction photovoltaic cell. The polymer introduces a strong electron-withdrawing group fluorine atom on an electron-deficient unit, thereby the HOMO energy level of the material can be effectively reduced, thereby the open-circuit voltage of the polymer photovoltaic cell can be enhanced.

Description

The conjugated polymers of 4,8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline
Technical field
The invention belongs to filed of functional, be specifically related to the conjugated polymers of a kind of 4,8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline and the application for the preparation of polymer photovoltaic cell thereof.
Background technology
The growth of socioeconomic development and population, consequent energy problem is day by day serious, develops reproducible new forms of energy extremely urgent.How sun power, as the inexhaustible green energy resource of one, effectively utilizes by its exploitation and by the mankind extensive concern that has been subject to international community.A kind of device-polymer solar battery converting solar energy into electrical energy, because preparation process is simple, cost is low, lightweight and can prepare the outstanding advantages such as flexible device, become in recent years domestic and international study hotspot, the focus of current polymer solar battery research is that the efficient conjugated polymers of exploitation improves its photovoltaic energy conversion efficiency to body and acceptor material.With regard to donor material, in order to obtain the polymer materials of superperformance, a kind of effective method is electron rich unit (D) and electron deficiency unit (A) alternately to be introduced to the main chain of conjugated polymers, give-acceptor (D-A-D) the type polymkeric substance of formation, this is the emphasis of studying to body polymkeric substance at present.
Quinoxaline and derivative thereof, as the novel short of electricity unit of a class, receive much concern in recent years and obtain synthetic TQ1 and the PCBM blend such as good performance, such as Ergang Wang, photoelectric transformation efficiency reaches 6.0%, [advanced material Adv.Mater.2010,22 (46), 5240-5244].The synthetic PECz-DTQX such as Cao Yong, with PCBM blend efficiency for reaching 6.07%, [advanced material Adv.Mater.2011,23 (27), 3086-3089].
Since 2009, fluorine atom is introduced into short of electricity unit because of having compared with strong electronegativity, by reducing the HOMO energy level of donor material and then the photoelectric transformation efficiency of boost device.The HOMO energy level of the synthetic PTB5 of the people such as such as Yu Luping be-5.01ev, the be reduced to-5.12ev of HOMO energy level of PTB4 after introducing fluorine atom, and open circuit voltage rises to 0.74V by 0.66V, [JACS J.Am.Chem.Soc.2009,131,7792-7799].The HOMO energy level of the synthetic PBnDT-HTAZ such as You Wei is-5.29eV, reduce to-the 5.36ev of HOMO energy level of (PBnDT-FTAZ) after introducing fluorine atom, open circuit voltage rises to 0.76V by 0.68V, [J.Am.Chem..Soc.2011,133 (12), 4625-4631].In view of other similar researchs such as above-mentioned theory, on this electron deficiency of quinoxaline unit, introduce fluorine atom and prepare novel fluorine-containing D-A-D type and be expected to obtain similar performance to body polymkeric substance, but yet there are no so far about the preparation method of this type of material and be applied to the report in photovoltaic cell.
Summary of the invention
A technical problem to be solved by this invention is that the D-A-D type that contains fluoro quinoxaline of development of new, to body polymer materials, meets the needs of polymer photovoltaic cell photoactive layers electron donor material.
For this reason, one 4 of the present invention, the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline, the general structure of this polymkeric substance is as shown in formula I:
In formula I,
R 1for: H atom or F atom;
R 2for: a position or para-position carbon atomicity are the alkoxy benzene of 4 to 20 straight or branched, or for carbonatoms be 2-alkylthrophene base or 2, the 3-dialkyl group thienyl of 4 to 20 straight or branched;
R 3for: H atom or for carbonatoms be the alkyl of 4 to 20 straight or branched.
Preferably (one), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline is as shown in formula II:
Preferably (two), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline is as shown in formula III:
Preferably (three), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline is as shown in formula IV:
Preferably (four), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline is suc as formula shown in (V):
Preferably (five), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline is as shown in formula VI:
Preferably (six), above-mentioned 4, the structural formula of the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline is suc as formula shown in (VII):
Another technical problem to be solved by this invention is above-mentioned 4,8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] conjugated polymers of bithiophene and fluoro quinoxaline is for the preparation of the application of polymer photovoltaic cell, to utilize the characteristic electron that draws of fluorine atom, by reducing the HOMO energy level of polymer materials, and then promote the open circuit voltage of photovoltaic cell.
Disclosed by the invention 4, the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline synthetic according to as shown in Scheme.1 polyreaction course carry out:
Concrete synthesis step is as follows:
(1) preparation of the fluorine-containing quinoxaline in short of electricity unit and derivative thereof
By 5 or 5,6 fluorine-containing 4,7-bis-bromo-2,1,3-diazosulfide is dissolved in dehydrated alcohol, adds sodium borohydride at 0 DEG C in batches, then under room temperature, react 20h, reaction finishes to concentrate removes ethanol, adds suitable quantity of water, ethyl acetate extraction, organic phase anhydrous magnesium sulfate drying, crude product silicagel column purifying obtains fluorinated diamine, then by fluorinated diamine and 1,2-, bis-R 2base second diketone is taking acetic acid as solvent reaction, make 6 or 6,7 fluorine-containing 5,8-bis-is bromo-2,3-bis-R 2base quinoxaline.
By above-mentioned 6 or 6,7 fluorine-containing 5,8-bis-is bromo-2,3-bis--R 2base quinoxaline and 4-R 3base thiophene tributyl tin is by Stille linked reaction, and products therefrom is taking DMF/THF as solvent, carries out bromo with NBS, obtain 6 or 6,7 fluorine-containing 5,8-bis-(the bromo-4-R of 5- 3base thiophene)-2, the disubstituted quinoxaline of 3-.
(2) preparation of polymkeric substance
This reaction is carried out under nitrogen protection, gets that a certain amount of replaced by 6 of body units fluorine-containing 5,8-bis-(the bromo-4-R of 5- 3base thiophene)-2, the two fluorine 5 of the disubstituted quinoxaline of 3-or 6,7-, 8-bis-(the bromo-4-R of 5- 3base thiophene)-2, the disubstituted quinoxaline of 3-, with 2 of equimolar amount, two (tin trimethyl)-4 of 6-, 8-bis-(5-iso-octyl thiophene) phenyl [1, 2-b:4, 5-b '] bithiophene, join in two mouthfuls of dry flasks, toluene dissolves, fluoro quinoxaline monomer concentration is controlled at 0.03mol/L left and right, after ventilation 0.5h, add catalyzer three (diphenylmethylene acetone) two palladiums of 0.02 times of molar weight and the part tri-o-tolyl phosphorus of 0.08 times of molar weight, continue ventilation 0.5h, then start heating, after back flow reaction 24h, stopped reaction, system is cooled to room temperature, reaction solution is splashed into sedimentation in methyl alcohol, filter, the 50 DEG C of baking 12h of polymkeric substance vacuum drying oven that collect, use successively methyl alcohol, normal hexane, chloroform carries out soxhlet extraction, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filter, obtain as shown in the formula (I) 4, 8-bis-(5-iso-octyl thiophene) phenyl [1, 2-b:4, 5-b '] conjugated polymers of bithiophene and fluoro quinoxaline.
Compared with prior art, the present invention adopts fluorine-containing quinoxaline and derivative thereof as short of electricity unit, 2 of symmetrical configuration, excellent property, two (tin trimethyl)-4 of 6-, 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene is as giving electric unit, synthesized single fluoro and two fluoro 4,8-bis-(5-iso-octyl thiophene) phenyl [1 by give-acceptor copolymerization mode, 2-b:4,5-b '] conjugated polymers of bithiophene and fluoro quinoxaline.Pass through cyclic voltammetry, with fluoro 4 not, 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] conjugated polymers (structural formula A ', B ' H and the C ' of bithiophene and quinoxaline, in table 1) compare, the HOMO energy level of single fluorinated polymer is the lower 0.02～0.2eV of fluoro, the lower 0.05-0.3eV of fluoro of two fluorinated polymer HOMO energy levels.Above-mentioned fluoro material and PCBM blended applications are in body heterojunction optical activity layer of polymer solar cell, and the open circuit voltage of device is at 0.6～1.0V.
Brief description of the drawings
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Fig. 1 be polymer A ' C-V figure;
Fig. 2 is the C-V figure of polymer A.
Embodiment
In order to understand better the present invention, and performance synthetic to this polymkeric substance is described in detail respectively below, institute
The example of act does not limit the scope of the invention.
Embodiment 1: polymer A
Step 1,6-is fluoro-5 in preparation, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(3-octyloxyphenyl) quinoxaline
Synthetic route is as follows:
(1) 4-is fluoro-3, and 6-bis-is bromo-1, the preparation of 2-phenylenediamine
5-is fluoro-4, and 7-bis-is bromo-2,1, and 3-diazosulfide (5g, 0.016mol) is dissolved in 150ml dehydrated alcohol, adds NaBH at 0 DEG C in batches 4(11.1g, 0.29mol), then reacts 20 under room temperature; After reaction finishes, concentrate and remove ethanol, add 160ml water, ethyl acetate extraction, saturated common salt water washing organic phase, anhydrous MgSO 4dry; Concentrated thick product eluent n-hexane/ethyl acetate (volume ratio of normal hexane and ethyl acetate the is 25:1) purification by silica gel column chromatography obtaining after organic solvent of removing, obtains 4-fluoro-3, and 6-bis-is bromo-1,2-phenylenediamine 3.5g, productive rate 78%.
The preparation of (2) 1,2-bis-(3-octyloxyphenyl) second diketone
To CuBr (4.33g, in THF solution (40ml) 30.2mmol), add LiBr (5.25g, 60.4mmol), stirring and dissolving under room temperature, under ice bath, temperature is down to 0 DEG C, start to drip new system between the Grignard reagent [bromobenzene octyl ether (8.6g of bromobenzene octyl ether, 30.2mmol), Mg (1g, 41.7mmol), THF (30ml)], after reaction 20min, start to drip oxalyl chloride (1.71g, 13.5mmol) at 0 DEG C, dropwise, continue to add saturated NH in the backward system of reaction 30min 4cl solution cancellation reaction, ethyl acetate extraction, saturated common salt water washing organic phase, anhydrous MgSO 4dry, the concentrated thick product purification by silica gel column chromatography obtaining after organic solvent of removing, washing and dehydrating integrated machine is n-hexane/ethyl acetate (volume ratio of normal hexane and ethyl acetate is 200:1), obtains 1,2-bis-(3-octyloxyphenyl) second diketone 3.46g, productive rate 55%.
(3) 6-is fluoro-5, and 8-bis-is bromo-2, the preparation of 3-bis-(3-octyloxyphenyl) quinoxaline
4-is fluoro-3, and 6-bis-is bromo-1, and 2-phenylenediamine (0.59g, 1.9mmol) and 1,2-bis-(3-octyloxyphenyl) second diketone (0.88g, 1.9mmol) is dissolved in 40mlHAc, is warming up to 60 DEG C, closes heating, under room temperature, reacts 2h; Suction filtration, washing with alcohol filter cake, obtains 6-fluoro-5, and 8-bis-is bromo-2,3-bis-(3-octyloxyphenyl) quinoxaline 1.31g, productive rate 97%. 1H?NMR(500MHz，CDCl3,ppm)：δ=7.97(d,1H),7.27(m,4H),7.21(t,2H),6.98(m,2H),3.9(t,4H)1.76(m,4H),1.45(dd,4H),1.34(m,16H),0.93(t,6H)。
(4) 6-is fluoro-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2, the preparation of 3-bis-(3-octyloxyphenyl) quinoxaline
6-is fluoro-5,8-bis-bromo-two (3-octyloxyphenyl) quinoxaline (0.821g, 1.15mmol), 4-hexyl-2-tributyl tin thiophene (1.124g, 2.46mmol) and Pd (PPh 3) Cl 2(0.032g, 0.046mmol) is dissolved in 20ml toluene, N 2the concentrated toluene of the lower back flow reaction 10～12h of protection, crude product normal hexane recrystallization, obtains safran solid 6-fluoro-5,8-bis-(4-hexyl thiophene)-2,3-bis-(3-octyloxyphenyl) quinoxaline (0.82g, 80%);
6-is fluoro-5,8-bis-(4-hexyl thiophene)-2, and 3-bis-(3-octyloxyphenyl) quinoxaline (0.62g, 0.7mmol), NBS (0.261g, 1.47mmol) is dissolved in 20mlDMF, 40 DEG C of reaction 7h; Cooling, suction filtration, methanol wash filter cake; Crude product normal hexane recrystallization, obtains 6-fluoro-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(3-octyloxy benzene) quinoxaline 0.48g, productive rate 65%;
1H?NMR(500MHz,CDCl 3,ppm):δ=7.91(d,1H),7.72(s,1H),7.55(dd,2H),7.50(S,1H),7.20(td,2H),7.09(M,2H),6.97(dt,2H),4.05(q,4H),2.64(td,4H),1.80(m,4H),1.66(m,4H),1.49(dd,4H)1.4-1.25(m,28H),0.9(m,12H)；
Step 2, two (tin trimethyl)-4 of preparation 2,6-, 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene
Synthetic route is as follows:
(1) prepare 4,8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene
Under nitrogen protection, 5-iso-octyl thiophene (7.25g, 37mmol) is dissolved in dry THF (30ml); when system is cooled to 0 DEG C, start to drip n-BuLi (2.2M, 41.2mmol); dropwise, be warming up to 50 DEG C of reaction 2h, add phenyl [1; 2-b:4; 5-b '] bithiophene-4,8-diketone (2.69g, 12.5mmol); at this temperature, react 1h, add subsequently SnCl 2h 2the mixed solution of O (22.6g, 99.8mmol) and dilute hydrochloric acid (2M, 30ml), continues after reaction 1.5h, and reactant is poured in frozen water, petroleum ether extraction, the anhydrous MgSO of organic phase 4dry; Thick product silica gel column chromatography, uses normal hexane wash-out, obtains 4,8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene (4.35g, 60%)
(2) prepare two (tin trimethyl)-4 of 2,6-, 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene
Whole reaction is carried out under nitrogen protection, 4,8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene (7.9g, 13.6mmol), be dissolved in 200mlTHF, be cooled to-80 DEG C, start to drip butyllithium (36.3mmol, 2.2M), dropwise, at-80 DEG C, react 1h, naturally rise to room temperature and continue reaction 1h, be again cooled to-80 DEG C, disposable trimethyltin chloride (the 8g that adds, THF(30ml 40.4mmol)) solution, remove cryostat, room temperature reaction 10～12h; Reaction solution is poured in 200ml water, n-hexane extraction, saturated common salt water washing organic phase, anhydrous MgSO 4dry; Crude product dehydrated alcohol recrystallization, obtains two (tin trimethyl)-4 of 2,6-, 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene (8.0g, 8.84mmol), productive rate 65%; 1hNMR (500MHz, CDCl 3, ppm): δ=7.72 (s, 2H), 7.31 (d, 2H), 6.85 (d, 2H), 2.88 (d, 4H), 1.75 (m, 2H), 1.57-1.24 (br, 16H), 0.88 (m, 12H), 0.41 (s, 18H)
Step 3, preparation polymer A
Synthetic route is as follows:
Whole reaction is carried out under nitrogen protection, 6-fluoro-5, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2, 3-bis-(3-octyloxyphenyl) quinoxaline (314mg, 0.3mmol) He 2, 6-bis-(tin trimethyl)-4, 8-bis-(5-iso-octyl thiophene) benzene 1,4-Dithiapentalene (271g, 0.3mmol) be dissolved in 20ml toluene, logical nitrogen 0.5h, add catalyzer three (diphenylmethylene acetone) two palladiums (5.5mg) and part tri-o-tolyl phosphorus (9.8mg), after ventilation 0.5h, start heating, back flow reaction 24h, by at room temperature naturally cooling of the polymkeric substance obtaining, dropwise add to sedimentation in methyl alcohol, filter, the polymkeric substance obtaining is used methyl alcohol successively, normal hexane, chloroform soxhlet extraction, concentrated chloroform extracted solution, again drop to sedimentation in methyl alcohol, obtain polymer A 300mg, for the fibrous solid of atropurpureus, productive rate 68.3%, number-average molecular weight 28542, molecular weight distribution 2.14.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag +electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile solvent, be that 0.56V(is referring to Fig. 2 through the initial oxidation current potential of cyclic voltammetry polymer A), polymer A ' initial oxidation current potential be that 0.47V(is referring to Fig. 1), can calculation formula-(4.72+ initial oxidation current potential/V) eV according to HOMO, the HOMO that obtains polymer A can be-5.28eV, than fluoro materials A not '-5.19eV, low 0.09eV, in table 1 and accompanying drawing.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymer A and acceptor material PC 61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.85V, photoelectric transformation efficiency is 4.05%.
Embodiment 2: polymer B
Synthetic route is as follows:
This embodiment is fluoro-5 with 6,7-bis-, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2, and 3-bis-(3-octyloxyphenyl) quinoxaline is short of electricity unit, adopts and prepares polymer B with the polymerization process in embodiment 1 step 3, productive rate 65%,
Number-average molecular weight 23129, molecular weight distribution 1.88.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag +electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymer B film can be-5.33eV, than fluoro materials A not '-5.19eV, low 0.14eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, makes photovoltaic cell by polymer B and acceptor material PC61BM according to certain weight ratio, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.91V, photoelectric transformation efficiency is 4.41%.
Embodiment 3: polymkeric substance C
Synthetic route is as follows:
This embodiment is fluoro-5 with 6-, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2, and 3-bis-(4-octyloxyphenyl) quinoxaline is short of electricity unit, adopt the method synthetic polymer C in embodiment 1 step 3, productive rate 72%, number-average molecular weight is 34752, molecular weight distribution 2.34.
Wherein adopt method in embodiment 1 step 1 to prepare 6-fluoro-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(4-octyloxyphenyl) quinoxaline.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag +electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance C film can be-5.23eV, than fluoro material B not '-5.15eV, low 0.08eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymkeric substance C and acceptor material PC 61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.85V, photoelectric transformation efficiency is 2.89%.
Embodiment 4: polymkeric substance D
Synthetic route is as follows:
This embodiment is with 6,7-bis-fluoro-5,8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(4-octyloxyphenyl) quinoxaline is short of electricity unit, adopt the synthesis step in embodiment 1 step 3 to prepare polymkeric substance D, productive rate 74.5%, number-average molecular weight is 35028, molecular weight distribution 2.43.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag +electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance D film can be-5.31eV, than fluoro material B not '-5.15eV, low 0.16eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, by polymkeric substance D and acceptor material PC 61bM makes photovoltaic cell according to certain weight ratio, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.89V, photoelectric transformation efficiency is 3.52%.
Embodiment 5: polymkeric substance E
Synthetic route is as follows:
This embodiment is fluoro-5 with 6-, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2, and 3-bis-(5-octyl group thiophene) quinoxaline is short of electricity unit, adopt the method in embodiment 1 step 3 to prepare polymkeric substance E, productive rate 84%, number-average molecular weight 40216, molecular weight distribution 1.76.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag +electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance E film can be-5.32eV, than fluoro material C not '-5.20eV, low 0.12eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, makes photovoltaic cell by polymkeric substance E and acceptor material PC61BM according to certain weight ratio, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.86V, photoelectric transformation efficiency is 3.85%.
Embodiment 6: polymkeric substance F
Synthetic route is as follows:
This embodiment is fluoro-5 with 6,7-bis-, 8-bis-(the bromo-4-hexyl thiophene of 5-)-2,3-bis-(5-octyl group thiophene) quinoxaline is short of electricity unit, adopts the method in embodiment 1 step 3 to prepare polymkeric substance F, productive rate 86%, number-average molecular weight 28644, molecular weight distribution 1.96.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag +electrode is reference electrode, Bu 4nPF 6make ionogen, in acetonitrile solvent, through the HOMO of cyclic voltammetry polymkeric substance F film can be-5.38eV, than fluoro material C not '-5.20eV, low 0.18eV, in table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 61the sandwich battery structure of BM/LiF/Al, makes photovoltaic cell by polymkeric substance F and acceptor material PC61BM according to certain weight ratio, useful area 0.0314cm 2, under Newport Thermal Oriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source table to gather, open circuit voltage is 0.92V, photoelectric transformation efficiency is 4.25%.
The HOMO energy level of table 1 polymkeric substance

Claims (4)

1. one kind 4, the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline, is characterized in that, the general structure of this polymkeric substance is as shown in formula I:
In formula I,
R 1for: H atom or F atom;
R 2for: carbonatoms is 2-alkylthrophene base or 2, the 3-dialkyl group thienyl of 4 to 20 straight or branched;
R 3for: carbonatoms is the alkyl of 4 to 20 straight or branched.
2. as claimed in claim 14, the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline, is characterized in that, the structural formula of this polymkeric substance is as shown in formula II:
3. as claimed in claim 14, the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline, is characterized in that, the structural formula of this polymkeric substance is as shown in formula III:
As described in arbitrary claim in claims 1 to 34, the conjugated polymers of 8-bis-(5-iso-octyl thiophene) phenyl [1,2-b:4,5-b '] bithiophene and fluoro quinoxaline is for the preparation of the application of polymer photovoltaic cell.
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